U.S. patent application number 11/666870 was filed with the patent office on 2008-12-25 for 2,6-diethyl-4-methylphenyl-substituted tetramic acid derivatives.
Invention is credited to Christian Arnold, Thomas Auler, Guido Bojack, Mark Wilhelm Drewes, Dieter Feucht, Reiner Fischer, Marin Jeffrey Hills, Heinz Kehne, Stefan Lehr, Olga Malsam, Chris Rosinger.
Application Number | 20080318776 11/666870 |
Document ID | / |
Family ID | 35506417 |
Filed Date | 2008-12-25 |
United States Patent
Application |
20080318776 |
Kind Code |
A1 |
Fischer; Reiner ; et
al. |
December 25, 2008 |
2,6-Diethyl-4-Methylphenyl-Substituted Tetramic Acid
Derivatives
Abstract
The invention relates to novel
2,6-diethyl-4-methylphenyl-substituted tetramic acid derivatives of
the formula (I) ##STR00001## in which A, B, D and G are as defined
above, to a plurality of processes and intermediates for their
preparation and to their use as pesticides and/or herbicides, and
also to selectively herbicidal compositions comprising, firstly,
the 2,6-diethyl-4-methylphenyl-substituted tetramic acid
derivatives of the formula (I) and, secondly, at least one crop
plant tolerance promoter compound.
Inventors: |
Fischer; Reiner; (Monheim,
DE) ; Lehr; Stefan; (Liederbach, DE) ; Drewes;
Mark Wilhelm; (Langenfeld, DE) ; Feucht; Dieter;
(Eschborn, DE) ; Malsam; Olga; (Rosrath, DE)
; Bojack; Guido; (Wiesbaden, DE) ; Arnold;
Christian; (Langenfeld, DE) ; Auler; Thomas;
(Leichlingen, DE) ; Hills; Marin Jeffrey;
(Idstein, DE) ; Kehne; Heinz; (Hofheim, DE)
; Rosinger; Chris; (Hofheim, DE) |
Correspondence
Address: |
STERNE, KESSLER, GOLDSTEIN & FOX P.L.L.C.
1100 NEW YORK AVENUE, N.W.
WASHINGTON
DC
20005
US
|
Family ID: |
35506417 |
Appl. No.: |
11/666870 |
Filed: |
October 21, 2005 |
PCT Filed: |
October 21, 2005 |
PCT NO: |
PCT/EP05/11343 |
371 Date: |
March 24, 2008 |
Current U.S.
Class: |
504/105 ;
504/106; 504/128; 504/138; 514/409; 514/91; 548/408; 548/413;
562/493 |
Current CPC
Class: |
C07D 209/54 20130101;
C07D 207/38 20130101; C07D 207/36 20130101; C07D 207/408
20130101 |
Class at
Publication: |
504/105 ;
548/408; 514/409; 514/91; 548/413; 504/138; 504/128; 504/106;
562/493 |
International
Class: |
A01N 25/32 20060101
A01N025/32; C07D 209/54 20060101 C07D209/54; A01N 43/38 20060101
A01N043/38; A01P 13/00 20060101 A01P013/00; C07C 51/06 20060101
C07C051/06; A01P 15/00 20060101 A01P015/00; A01N 57/16 20060101
A01N057/16; C07F 9/572 20060101 C07F009/572 |
Foreign Application Data
Date |
Code |
Application Number |
Nov 4, 2004 |
DE |
10 2004 053 191.9 |
Claims
1. A compound of the formula (I) ##STR00109## in which A represents
hydrogen, in each case optionally halogen-substituted alkyl,
alkenyl, alkoxyalkyl or alkylthioalkyl or optionally substituted
cycloalkyl, 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 C.sub.3-C.sub.8-ring which optionally
contains at least one heteroatom and which is optionally
substituted and D represents hydrogen, or A represents hydrogen or
alkyl, B represents hydrogen and D represents an optionally
substituted radical selected from the group consisting of alkyl,
alkenyl, alkynyl, alkoxyalkyl, alkylthioalkyl and cycloalkyl, or A
and D together with the atoms to which they are attached represent
a saturated or unsaturated cycle which optionally contains at least
one oxygen or sulfur atom in the A,D moiety or which is optionally
substituted by alkyl, alkoxy or haloalkyl, and G represents one of
the groups ##STR00110## in which E represents a metal ion
equivalent or an ammonium iron, L represents oxygen or sulfur, M
represents oxygen or sulfur, R.sup.1 represents in each case
optionally substituted primary or secondary alkyl, alkenyl,
alkoxyalkyl, alkylthioalkyl or polyalkoxyalkyl, or in each case
optionally halogen-, alkyl- or alkoxy-substituted cycloalkyl or
heterocyclyl, or in each case optionally substituted phenyl or
heteroaryl, R.sup.2 represents in each case optionally
halogen-substituted alkyl, alkenyl, alkoxy-alkyl or
polyalkoxyalkyl, or in each case optionally substituted cycloalkyl,
phenyl or benzyl, R.sup.3, R.sup.4 and R.sup.5 independently of one
another represent in each case optionally halogen-substituted
alkyl, alkoxy, alkylamino, dialkylamino, alkylthio, alkenylthio or
cycloalkylthio, or in each case optionally substituted phenyl,
benzyl, phenoxy or phenylthio, R.sup.6 and R.sup.7 independently of
one another represent hydrogen, in each case optionally
halogen-substituted alkyl, cycloalkyl, alkenyl, alkoxy,
alkoxyalkyl, in each case optionally substituted phenyl or benzyl
or together with the N-atom to which they are attached form an
optionally substituted cycle which optionally contains oxygen or
sulfur.
2. A compound according to claim 1 in which A represents hydrogen,
C.sub.1-C.sub.8-alkyl, C.sub.2-C.sub.8-alkenyl,
C.sub.2-C.sub.8-alkoxy-C.sub.1-C.sub.4-alkyl or
C.sub.1-C.sub.6-alkylthio-C.sub.1-C.sub.4-alkyl, each of which is
optionally mono- to trisubstituted by halogen, or
C.sub.3-C.sub.8-cycloalkyl which is optionally mono- to
trisubstituted by halogen, C.sub.1-C.sub.6-alkyl or
C.sub.1-C.sub.6-alkoxy, B represents hydrogen,
C.sub.1-C.sub.6-alkyl or
C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.2-alkyl, or A, B and the
carbon atom to which they are attached represent saturated
C.sub.3-C.sub.8-cycloalkyl or unsaturated
C.sub.5-C.sub.8-cycloalkyl in which optionally one methylene group
is replaced by oxygen or sulfur and which is optionally substituted
by C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.4-haloalkyl or
C.sub.1-C.sub.6-alkoxy, and D represents hydrogen, or A represents
hydrogen or C.sub.1-C.sub.8-alkyl, B represents hydrogen and D
represents C.sub.1-C.sub.8-alkyl, C.sub.1-C.sub.8-alkenyl,
C.sub.1-C.sub.6-alkoxy-C.sub.2-C.sub.4-alkyl or
C.sub.1-C.sub.6alkylthio-C.sub.2-C.sub.4-alkyl, each of which is
optionally mono- to pentasubstituted by halogen, or represents
C.sub.3-C.sub.8-cycloalkyl which is optionally mono- to
trisubstituted by halogen, C.sub.1-C.sub.4-alkyl,
C.sub.1-C.sub.4-alkoxy or C.sub.1-C.sub.2-haloalkyl, or A and D
together represent a C.sub.3-C.sub.6-alkanediyl or
C.sub.3-C.sub.6-alkenediyl group in which in each case optionally
one methylene group is replaced by oxygen or sulfur and which is in
each case mono- to disubstituted by C.sub.1-C.sub.4-alkyl,
C.sub.1-C.sub.4-alkoxy or C.sub.1-C.sub.4-haloalkyl or by a further
C.sub.3-C.sub.6-alkanediyl, C.sub.3-C.sub.6-alkenediyl- or
C.sub.4-C.sub.6-alkanedienediyl group which forms a fused-on ring,
G represents one of the groups ##STR00111## in which E represents a
metal ion equivalent or an ammonium iron, L represents oxygen or
sulfur and M represents oxygen or sulfur, R.sup.1 represents
primary or secondary C.sub.1-C.sub.20-alkyl,
C.sub.2-C.sub.20-alkenyl,
C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-alkylthio-C.sub.1-C.sub.6-alkyl or
poly-C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.4-alkyl, each of which is
optionally mono- to heptasubstituted by halogen, mono- to
disubstituted by cyano, monosubstituted by COR.sup.13,
C.dbd.N--OR.sup.13, CO.sub.2R.sup.13 ##STR00112## or represents
C.sub.3-C.sub.8-cycloalkyl which is optionally mono- to
trisubstituted by halogen, C.sub.1-C.sub.4-alkyl or
C.sub.1-C.sub.4-alkoxy and in which optionally one or two not
directly adjacent methylene groups are replaced by oxygen or
sulfur, represents phenyl, phenyl-C.sub.1-C.sub.2-alkyl or
phenyl-C.sub.1-C.sub.2-alkenyl, each of which is optionally mono-
to trisubstituted by halogen, cyano, nitro, C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-haloalkyl,
C.sub.1-C.sub.6-haloalkoxy, C.sub.1-C.sub.6-alkylthio,
C.sub.1-C.sub.6-alkylsulfinyl or C.sub.1-C.sub.6-alkylsulfonyl,
represents 5- or 6-membered heteroaryl which is optionally mono- to
disubstituted by halogen or C.sub.1-C.sub.6-alkyl substituents and
which has one or two heteroatoms selected from the group consisting
of oxygen, sulfur and nitrogen, R.sup.2 represents
C.sub.1-C.sub.20-alkyl, C.sub.2-C.sub.20-alkenyl,
C.sub.1-C.sub.6-alkoxy-C.sub.2-C.sub.6-alkyl or
poly-C.sub.1-C.sub.6-alkoxy-C.sub.2-C.sub.6-alkyl, each of which is
optionally mono- to trisubstituted by halogen, or represents
C.sub.3-C.sub.8-cycloalkyl which is optionally mono- to
disubstituted by halogen, C.sub.1-C.sub.6-alkyl or
C.sub.1-C.sub.6-alkoxy or represents phenyl or benzyl, each of
which is optionally mono- to trisubstituted by halogen, cyano,
nitro, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.6-haloalkyl or C.sub.1-C.sub.6-haloalkoxy, R.sup.3
represents C.sub.1-C.sub.8-alkyl which is optionally mono- to
polysubstituted by halogen, or phenyl or benzyl, each of which is
optionally mono- to disubstituted by halogen,
C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.4-haloalkyl, C.sub.1-C.sub.4-haloalkoxy, cyano or
nitro, R.sup.4 and R.sup.5 independently of one another represent
C.sub.1-C.sub.8-alkyl, C.sub.1-C.sub.8-alkoxy,
C.sub.1-C.sub.8-alkylamino, di(C.sub.1-C.sub.8-alkyl)amino,
C.sub.1-C.sub.8-alkylthio or C.sub.2-C.sub.8-alkenyl-thio, each of
which is optionally mono- to trisubstituted by halogen, or
represent phenyl, phenoxy or phenylthio, each of which is
optionally mono- to trisubstituted by halogen, nitro, cyano,
C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.4-haloalkoxy,
C.sub.1-C.sub.4-alkylthio, C.sub.1-C.sub.4-haloalkylthio,
C.sub.1-C.sub.4-alkyl or C.sub.1-C.sub.4-haloalkyl, R.sup.6 and
R.sup.7 independently of one another represent hydrogen,
C.sub.1-C.sub.8-alkyl, C.sub.3-C.sub.8-cycloalkyl,
C.sub.1-C.sub.8-alkoxy, C.sub.3-C.sub.8-alkenyl or
C.sub.1-C.sub.8-alkoxy-C.sub.2-C.sub.8-alkyl, each of which is
optionally mono- or trisubstituted by halogen, or represent phenyl
or benzyl, each of which is optionally mono- to trisubstituted by
halogen, C.sub.1-C.sub.8-alkyl, C.sub.1-C.sub.8-haloalkyl or
C.sub.1-C.sub.8-alkoxy, or together represent a
C.sub.3-C.sub.6-alkylene radical which is optionally mono- to
disubstituted by C.sub.1-C.sub.4-alkyl and in which optionally one
methylene group is replaced by oxygen or sulfur, R.sup.13
represents C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-alkenyl,
C.sub.3-C.sub.6-alkynyl or
C.sub.1-C.sub.4-alkoxy-C.sub.2-C.sub.4-alkyl, each of which is
optionally mono- to trisubstituted by halogen, or represents
C.sub.3-C.sub.6-cycloalkyl which is optionally mono- to
disubstituted by halogen, C.sub.1-C.sub.2-alkyl or
C.sub.1-C.sub.2-alkoxy and in which optionally one or two not
directly adjacent methylene groups are replaced by oxygen, or
represents phenyl or phenyl-C.sub.1-C.sub.2-alkyl, each of which is
optionally mono- to disubstituted by fluorine, chlorine, bromine,
C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy,
C.sub.1-C.sub.2-haloalkyl, C.sub.1-C.sub.2-haloalkoxy, cyano or
nitro, R.sup.13' represents hydrogen, C.sub.1-C.sub.6-alkyl or
C.sub.3-C.sub.6-alkenyl.
3. A compound according to claim 1 in which A represents hydrogen,
C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.3-alkyl or
C.sub.1-C.sub.4-alkylthio-C.sub.1-C.sub.3-alkyl, each of which is
optionally mono- to trisubstituted by fluorine or chlorine, or
represents C.sub.3-C.sub.6-cycloalkyl which is optionally mono- to
disubstituted by fluorine, chlorine, C.sub.1-C.sub.2-alkyl or
C.sub.1-C.sub.2-alkoxy, B represents hydrogen,
C.sub.1-C.sub.4-alkyl or
C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.2-alkyl, or A, B and the
carbon atom to which they are attached represent saturated
C.sub.3-C.sub.7-cycloalkyl in which optionally one methylene group
is replaced by oxygen and which is optionally mono- to
disubstituted by C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.2-haloalkyl
or C.sub.1-C.sub.4-alkoxy, and D represents hydrogen, or A
represents hydrogen or C.sub.1-C.sub.6-alkyl, B represents hydrogen
and D represents C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-alkenyl,
C.sub.1-C.sub.4-alkoxy-C.sub.2-C.sub.3-alkyl or
C.sub.1-C.sub.4-alkylthio-C.sub.2-C.sub.3-alkyl, each of which is
optionally mono- to trisubstituted by fluorine or chlorine, or
represents C.sub.3-C.sub.6-cycloalkyl which is optionally mono- to
disubstituted by fluorine, chlorine, C.sub.1-C.sub.2-alkyl,
C.sub.1-C.sub.2-alkoxy or trifluoromethyl, or A and D together
represent a C.sub.3-C.sub.5-alkanediyl group in which optionally
one methylene group is replaced by oxygen or sulfur and which is
optionally mono- to disubstituted by C.sub.1-C.sub.2-alkyl,
C.sub.1-C.sub.2-alkoxy or trifluoromethyl, or A and D together with
the atoms to which they are attached represent one of the groups
AD-1 to AD-10 ##STR00113## G represents one of the groups
##STR00114## in which E represents a metal ion equivalent or an
ammonium ion, L represents oxygen or sulfur and M represents oxygen
or sulfur, R.sup.1 represents primary or secondary
C.sub.1-C.sub.10-alkyl, C.sub.2-C.sub.10-alkenyl,
C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.2-alkyl,
C.sub.1-C.sub.4-alkylthio-C.sub.1-C.sub.2-alkyl or
poly-C.sub.1-C.sub.3-alkoxy-C.sub.1-C.sub.2-alkyl, each of which is
optionally mono- to pentasubstituted by fluorine or chlorine,
monosubstituted by cyano or, monosubstituted by CO--R.sup.13,
C.dbd.N--OR.sup.13 or CO.sub.2R.sup.13, or represents
C.sub.3-C.sub.6-cycloalkyl which is optionally mono- to
disubstituted by fluorine, chlorine, C.sub.1-C.sub.2-alkyl or
C.sub.1-C.sub.2-alkoxy and in which optionally one or two not
directly adjacent methylene groups are replaced by oxygen, or
represents phenyl or benzyl, each of which is optionally mono- to
disubstituted by fluorine, chlorine, bromine, cyano, nitro,
C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkylthio,
C.sub.1-C.sub.4-alkylsulfinyl, C.sub.1-C.sub.4-alkylsulfonyl,
C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.2-haloalkyl or
C.sub.1-C.sub.2-haloalkoxy, or represents pyrazolyl, thiazolyl,
pyridyl, pyrimidyl, furanyl or thienyl, each of which is optionally
mono- to disubstituted by fluorine, chlorine, bromine or
C.sub.1-C.sub.2-alkyl, R.sup.2 represents C.sub.1-C.sub.10-alkyl,
C.sub.2-C.sub.10-alkenyl,
C.sub.1-C.sub.4-alkoxy-C.sub.2-C.sub.4-alkyl or
poly-C.sub.1-C.sub.4-alkoxy-C.sub.2-C.sub.4-alkyl, each of which is
optionally mono- to trisubstituted by fluorine or chlorine, or
represents C.sub.3-C.sub.7-cycloalkyl which is optionally
monosubstituted by C.sub.1-C.sub.2-alkyl or C.sub.1-C.sub.2-alkoxy,
or represents phenyl or benzyl, each of which is optionally mono-
to disubstituted by fluorine, chlorine, bromine, cyano, nitro,
C.sub.1-C.sub.4-alkyl, methoxy, trifluoromethyl or
trifluoromethoxy, R.sup.3 represents C.sub.1-C.sub.4-alkyl which is
optionally mono- to trisubstituted by fluorine or chlorine or
represents phenyl or benzyl, each of which is optionally
monosubstituted by fluorine, chlorine, bromine,
C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy, trifluoromethyl,
trifluoromethoxy, cyano or nitro, R.sup.4 and R.sup.5 independently
of one another represent C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-alkylamino,
di(C.sub.1-C.sub.6-alkyl)amino, C.sub.1-C.sub.6-alkylthio or
C.sub.3-C.sub.4-alkenylthio, each of which is optionally mono- to
trisubstituted by fluorine or chlorine, or represent phenyl,
phenoxy or phenylthio, each of which is optionally mono- to
disubstituted by fluorine, chlorine, bromine, nitro, cyano,
C.sub.1-C.sub.3-alkoxy, trifluoromethoxy,
C.sub.1-C.sub.3-alkylthio, C.sub.1-C.sub.3-alkyl or
trifluoromethyl, R.sup.6 and R.sup.7 independently of one another
represent hydrogen, C.sub.1-C.sub.6-alkyl,
C.sub.3-C.sub.6-cycloalkyl, C.sub.1-C.sub.4-alkoxy,
C.sub.3-C.sub.6-alkenyl or
C.sub.1-C.sub.6-alkoxy-C.sub.2-C.sub.6-alkyl, each of which is
optionally mono- to trisubstituted by fluorine or chlorine, or
represent phenyl which is optionally mono- to disubstituted by
fluorine, chlorine, bromine, trifluoromethyl, C.sub.1-C.sub.4-alkyl
or C.sub.1-C.sub.4-alkoxy, or together represent a
C.sub.5-C.sub.6-alkylene radical which is optionally mono- to
disubstituted by methyl in which optionally one methylene group is
replaced by oxygen, R.sup.13 represents C.sub.1-C.sub.4-alkyl,
C.sub.3-C.sub.4-alkenyl, C.sub.3-C.sub.4-alkynyl, or
C.sub.1-C.sub.4-alkoxy-C.sub.2-C.sub.3-alkyl, or represents
C.sub.3-C.sub.6-cycloalkyl in each optionally one methylene group
is replaced by oxygen.
4. A compound according to claim 1 in which A represents hydrogen,
methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl,
tert-butyl, trifluoromethyl, methoxymethyl, ethoxymethyl,
cyclo-propyl, cyclopentyl or cyclohexyl, B represents hydrogen,
methyl or ethyl, or A, B and the carbon atom to which they are
attached represent saturated C.sub.6-cycloalkyl in which optionally
one methylene group is replaced by oxygen and which is optionally
substituted by methyl, ethyl, trifluoromethyl, methoxy, ethoxy,
n-propoxy, n-butoxy or isobutoxy, and D represents hydrogen, or A
represents hydrogen, methyl or ethyl, B represents hydrogen, and D
represents methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl,
isobutyl, cyclopropyl, cyclopentyl or cyclohexyl, or A and D
together represent a C.sub.3-C.sub.4-alkanediyl group in which
optionally one methylene group is replaced by oxygen or sulfur and
which is optionally mono- to disubstituted by methyl or methoxy, or
A and D together with the atoms to which they are attached
represent the groups below: ##STR00115## G represents one of the
groups ##STR00116## L represents oxygen and M represents oxygen or
sulfur, R.sup.1 represents primary or secondary
C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.1-C.sub.2-alkoxy-C.sub.1-C.sub.2-alkyl,
C.sub.1-C.sub.2-alkylthio-C.sub.1-C.sub.2-alkyl or
poly-C.sub.1-C.sub.2-alkoxy-C.sub.1-C.sub.2-alkyl, each of which is
optionally mono- to trisubstituted by fluorine or chlorine, or
represents cyclopropyl, cyclopentyl or cyclohexyl, each of which is
optionally monosubstituted by fluorine, chlorine, methyl, ethyl or
methoxy, or represents phenyl which is optionally monosubstituted
by fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl,
n-propyl, isopropyl, methoxy, ethoxy, methylthio, ethylthio,
methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl,
trifluoromethyl or trifluoromethoxy, or represents furanyl, thienyl
or pyridyl, each of which is optionally monosubstituted by
chlorine, bromine or methyl, R.sup.2 represents
C.sub.1-C.sub.8-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.1-C.sub.3-alkoxy-C.sub.2-C.sub.3-alkyl, cyclopentyl or
cyclohexyl, or represents phenyl or benzyl, each of which is
optionally monosubstituted by fluorine, chlorine, bromine, cyano,
nitro, methyl, methoxy, trifluoromethyl or trifluoromethoxy,
R.sup.4 represents C.sub.1-C.sub.6-alkoxy, R.sup.5 represents
C.sub.1-C.sub.6-alkoxy, R.sup.6 represents hydrogen,
C.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.6-cycloalkyl or allyl, or
represents phenyl which is optionally monosubstituted by fluorine,
chlorine, bromine, methyl, methoxy or trifluoromethyl, R.sup.7
represents methyl, ethyl, n-propyl, isopropyl or allyl, R.sup.6 and
R.sup.7 together represent a C.sub.5-C.sub.6-alkylene radical in
which optionally one methylene group is replaced by oxygen.
5. A compound according to claim 1 in which A represents methyl,
ethyl or cyclopropyl, B represents methyl or ethyl, or A, B and the
carbon atom to which they are attached represent saturated
C.sub.6-cycloalkyl which is optionally substituted by methyl or
methoxy, D represents hydrogen, or A represents methyl or ethyl, B
represents hydrogen, D represents methyl, ethyl or cyclopropyl, or
A and D together represent a C.sub.3-C.sub.4-alkanediyl group which
is optionally monosubstituted by methoxy, or A and D together with
the atoms to which they are attached represent the groups AD-1 and
AD-2, ##STR00117## G represents one of the groups ##STR00118##
R.sup.1 represents primary or secondary C.sub.1-C.sub.6-alkyl,
C.sub.2-C.sub.6-alkenyl,
C.sub.1-C.sub.2-alkoxy-C.sub.1-C.sub.2-alkyl,
C.sub.1-C.sub.2-alkylthio-C.sub.1-C.sub.2-alkyl or
poly-C.sub.1-C.sub.2-alkoxy-C.sub.1-C.sub.2-alkyl, each of which is
optionally mono- to trisubstituted by fluorine or chlorine, or
represents cyclopropyl, cyclopentyl or cyclohexyl, each of which is
optionally monosubstituted by fluorine, chlorine, methyl, ethyl or
methoxy, or represents phenyl which is optionally monosubstituted
by fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl,
n-propyl, isopropyl, methoxy, ethoxy, methylthio, ethylthio,
methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl,
trifluoromethyl or trifluoromethoxy, or represents furanyl, thienyl
or pyridyl, each of which is optionally monosubstituted by
chlorine, bromine or methyl, R.sup.2 represents
C.sub.1-C.sub.8-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.1-C.sub.3-alkoxy-C.sub.2-C.sub.3-alkyl, cyclopentyl or
cyclohexyl, or or represents phenyl or benzyl, each of which is
optionally monosubstituted by fluorine, chlorine, bromine, cyano,
nitro, methyl, methoxy, trifluoromethyl or trifluoromethoxy,
R.sup.4 represents C.sub.1-C.sub.6-alkoxy, and R.sup.5 represents
C.sub.1-C.sub.6-alkoxy.
6. A process for preparing a compound according to claim 1
comprising (A) obtaining a compound of the formula (I-b)
##STR00119## in which A, B, D and R.sup.1 are as defined in claim 1
by reacting a compound of the formula (I-a) ##STR00120## in which
A, B and D are as defined in claim 1 a) with an acid halide of the
formula (II) ##STR00121## in which R.sup.1 is as defined above and
Hal represents halogen or b) with a carboxylic anhydride of the
formula (III) R.sup.1--CO--O--CO--R.sup.1 (III) in which R.sup.1 is
as defined above, optionally in the presence of a diluent and
optionally in the presence of an acid binder, or (B) obtaining a
compound of the formula (I-c) ##STR00122## in which A, B, D,
R.sup.2 and M are as defined in claim 1 and L represents oxygen by
reacting a compound of the formula (I-a) shown above in which A, B
and D are as defined above with a chloroformic ester or a
chloroformic thioester of the formula (IV) R.sup.2-M-CO--Cl (IV) in
which R.sup.2 and M are as defined above, optionally in the
presence of a diluent and optionally in the presence of an acid
binder, or (C) obtaining a compound of the formula (I-c) by
reacting a compound of the formula (I-a) shown above in which A, B
and D are as defined above a) with a chloromonothioformic ester or
a chlorodithioformic ester of the formula (V) ##STR00123## in which
M and R.sup.2 are as defined above, optionally in the presence of a
diluent and optionally in the presence of an acid binder, or b)
with carbon disulfide and then with a compound of the formula (VI)
R.sup.2--Hal (VI) in which R.sup.2 is as defined above and Hal
represents chlorine, bromine or iodine, optionally in the presence
of a diluent and optionally in the presence of a base, or D)
obtaining a compound of the formula (I-d) ##STR00124## in which A,
B, D and R.sup.3 are as defined in claim 1 by reacting a compound
of the formula (I-a) shown above in which A, B and D are as defined
above with a sulfonyl chloride of the formula (VII)
R.sup.3--SO.sub.2--Cl (VII) in which R.sup.3 is as defined above,
optionally in the presence of a diluent and optionally in the
presence of an acid binder, or (E) obtaining a compound of the
formula (I-e) ##STR00125## in which A, B, D, L, R.sup.4 and R.sup.5
are as defined in claim 1 by reacting a compound of the formula
(I-a) shown above in which A, B and D are as defined above with a
phosphorus compound of the formula (VIII), ##STR00126## in which L,
R.sup.4 and R.sup.5 are as defined above and Hal represents
halogen, optionally in the presence of a diluent and optionally in
the presence of an acid binder, or (F) obtaining a compound of the
formula (I-f) ##STR00127## in which A, B, D and E are as defined in
claim 1 by reacting a compound of the formula (I-a) shown above in
which A, B and D are as defined above with a metal compound or an
amine of the formulae (IX) or (X), ##STR00128## 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
represent hydrogen or alkyl, optionally in the presence of a
diluent, or (G) obtaining a compound of the formula (I-g)
##STR00129## in which A, B, D, L, R.sup.6 and R.sup.7 are as
defined in claim 1 by reacting a compound of the formula (I-a)
shown above in which A, B and D are as defined above a) with an
isocyanate or an isothiocyanate of the formula (XI),
R.sup.6--N.dbd.C=L (XI) in which R.sup.6 and L are as defined
above, optionally in the presence of a diluent and optionally in
the presence of a catalyst, or b) with a carbamoyl chloride or a
thiocarbamoyl chloride of the formula (XII), ##STR00130## in which
L, R.sup.6 and R.sup.7 are as defined above, optionally in the
presence of a diluent and optionally in the presence of an acid
binder.
7. A composition comprising an effective amount of an active
compound combination comprising, as components, a') at least one
compound according to claim 1 or b') at least one substituted
cyclic ketoenol of the formula (I-a) ##STR00131## in which A
represents hydrogen, C.sub.2-C.sub.10-alkyl,
C.sub.1-C.sub.6-haloalkyl, in each case optionally
halogen-substituted alkenyl, alkoxyalkyl or alkylthioalkyl, or
optionally substituted cycloalkyl, 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
C.sub.3-C.sub.8-ring which is substituted by alkyl, alkoxy or
haloalkyl, or a C.sub.5-C.sub.8-ring which contains at least one
heteroatom and which is optionally substituted, and D represents
hydrogen or A represents hydrogen or alkyl, B represents hydrogen
and D represents an optionally substituted radical selected from
the group consisting of C.sub.2-C.sub.10-alkyl, alkenyl, alkynyl,
alkoxyalkyl, alkylthioalkyl and substituted cycloalkyl, or A and D
together with the atoms to which they are attached represent a
saturated or unsaturated cycle which optionally contains at least
one oxygen or sulfur atom in the A,D-moiety and which is optionally
substituted by alkyl, alkoxy or haloalkyl, and (c') at least one
crop plant tolerance promoter compound selected from the group
consisting of: 4-dichloroacetyl-1-oxa-4-azaspiro[4.5]decane (AD-67,
MON-4660),
1-dichloroacetylhexahydro-3,3,8a-trimethylpyrrolo[1,2-a]pyrimidin-6(2H)-o-
ne (dicyclonon, BAS-145138),
4-dichloroacetyl-3,4-dihydro-3-methyl-2H-1,4-benzoxazine
(benoxacor), 1-methylhexyl 5-chloroquinoline-8-oxyacetate
(cloquintocet-mexyl),
3-(2-chlorobenzyl)-1-(1-methyl-1-phenylethyl)urea (cumyluron),
.alpha.-(cyanomethoximino)phenylacetonitrile (cyometrinil),
2,4-dichlorophenoxyacetic acid (2,4-D),
4-(2,4-dichlorophenoxy)butyric acid (2,4-DB),
1-(1-methyl-1-phenylethyl)-3-(4-methylphenyl)urea (daimuron,
dymron), 3,6-dichloro-2-methoxybenzoic acid (dicamba),
S-1-methyl-1-phenylethyl piperidine-1-thiocarboxylate
(dimepiperate),
2,2-dichloro-N-(2-oxo-2-(2-propenylamino)ethyl)-N-(2-propenyl)-acetamide
(DKA-24), 2,2-dichloro-N,N-di-2-propenylacetamide (dichlormid),
4,6-dichloro-2-phenylpyrimidine (fenclorim), ethyl
1-(2,4-dichlorophenyl)-5-trichloromethyl-1H-1,2,4-triazole-3-carboxylate
(fenchlorazole-ethyl), phenylmethyl
2-chloro-4-trifluoromethylthiazole-5-carboxylate (flurazole),
4-chloro-N-(1,3-dioxolan-2-ylmethoxy)-.alpha.-trifluoroacetophenone
oxime (fluxofenim),
3-dichloroacetyl-5-(2-furanyl)-2,2-dimethyloxazolidine (furilazole,
MON-13900), ethyl 4,5-dihydro-5,5-diphenyl-3-isoxazolecarboxylate
(isoxadifen-ethyl), 1-(ethoxycarbonyl)ethyl
3,6-dichloro-2-methoxybenzoate (lactidichlor),
(4-chloro-o-tolyloxy)acetic acid (MCPA),
2-(4-chloro-o-tolyloxy)propionic acid (mecoprop), diethyl
1-(2,4-dichoro-phenyl)-4,5-dihydro-5-methyl-1H-pyrazole-3,5-dicarboxylate
(mefenpyr-diethyl), 2-dichloromethyl-2-methyl-1,3-dioxolane
(MG-191), 2-propenyl-1-oxa-4-azaspiro[4.5]decane-4-carbodithioate
(MG-838), 1,8-naphthalic anhydride,
.alpha.-(1,3-dioxolan-2-ylmethoximino)phenylacetonitrile
(oxabetrinil),
2,2-dichloro-N-(1,3-dioxolan-2-ylmethyl)-N-(2-propenyl)acetamide
(PPG-1292), 3-dichloroacetyl-2,2-di-methyloxazolidine (R-28725),
3-dichloroacetyl-2,2,5-trimethyloxazolidine (R-29148),
4-(4-chloro-o-tolyl)butyric acid, 4-(4-chlorophenoxy)butyric acid,
diphenylmethoxyacetic acid, methyl diphenylmethoxyacetate, ethyl
diphenylmethoxyacetate, methyl
1-(2-chlorophenyl)-5-phenyl-1H-pyrazole-3-carboxylate, ethyl
1-(2,4-dichlorophenyl)-5-methyl-1H-pyrazole-3-carboxylate, ethyl
1-(2,4-dichlorophenyl)-5-isopropyl-1H-pyrazole-3-carboxylate, ethyl
1-(2,4-dichlorophenyl)-5-(1,1-dimethyl-ethyl)-1H-pyrazole-3-carboxylate,
ethyl 1-(2,4-dichlorophenyl)-5-phenyl-1H-pyrazole-3-carboxylate,
ethyl 5-(2,4-dichlorobenzyl)-2-isoxazoline-3-carboxylate, ethyl
5-phenyl-2-isoxazoline-3-carboxylate, ethyl
5-(4-fluorophenyl)-5-phenyl-2-isoxazoline-3-carboxylate,
1,3-dimethylbut-1-yl 5-chloroquinoline-8-oxyacetate,
4-allyloxybutyl 5-chloroquinoline-8-oxyacetate, 1-allyloxyprop-2-yl
5-chloroquinoline-8-oxyacetate, methyl
5-chloroquinoxaline-8-oxyacetate, ethyl
5-chloroquinoline-8-oxyacetate, allyl
5-chloroquinoxaline-8-oxyacetate, 2-oxoprop-1-yl
5-chloroquinoline-8-oxyacetate, diethyl
5-chloroquinoline-8-oxymalonate, diallyl
5-chloroquinoxaline-8-oxymalonate, diethyl
5-chloroquinoline-8-oxymalonate, 4-carboxychroman-4-ylacetic acid
(AC-304415), 4-chlorophenoxyacetic acid,
3,3'-dimethyl-4-methoxybenzophenone,
1-bromo-4-chloromethylsulfonylbenzene,
1-[4-(N-2-methoxybenzoylsulfamoyl)phenyl]-3-methylurea (also known
as
N-(2-methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide),
1-[4-(N-2-methoxy-benzoylsulfamoyl)phenyl]-3,3-dimethylurea,
1-[4-(N-4,5-dimethyl-benzoylsulfamoyl)phenyl]-3-methylurea,
1-[4-(N-naphthylsulfamoyl)-phenyl]-3,3-dimethylurea,
N-(2-methoxy-5-methylbenzoyl)-4-(cyclopropylaminocarbonyl)benzenesulfonam-
ide, or one of the following compounds, of formula (IIa)
##STR00132## or of formula (IIb) ##STR00133## or of formula (IIc)
##STR00134## where m represents a number 0, 1, 2, 3, 4 or 5,
A.sup.1 represents one of the divalent heterocyclic groupings shown
below ##STR00135## n represents a number 0, 1, 2, 3, 4 or 5,
A.sup.2 represents optionally C.sub.1-C.sub.4-alkyl- or
C.sub.1-C.sub.4-alkoxy-carbonyl- or
C.sub.1-C.sub.4-alkenyloxy-carbonyl-substituted alkanediyl having 1
or 2 carbon atoms, R.sup.14 represents hydroxyl, mercapto, amino,
C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-alkylthio,
C.sub.1-C.sub.6-alkylamino or di(C.sub.1-C.sub.4-alkyl)amino,
R.sup.15 represents hydroxyl, mercapto, amino,
C.sub.1-C.sub.7-alkoxy, C.sub.1-C.sub.6-alkenyloxy,
C.sub.1-C.sub.6-alkenyloxy-C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.6-alkylthio, C.sub.1-C.sub.6-alkylamino or
di(C.sub.1-C.sub.4-alkyl)-amino, R.sup.16 represents optionally
fluorine-, chlorine- or bromine-substituted C.sub.1-C.sub.4-alkyl,
R.sup.17 represents hydrogen, in each case optionally fluorine-,
chlorine- or bromine-substituted C.sub.1-C.sub.6-alkyl,
C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl,
C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.4-alkyl,
dioxolanyl-C.sub.1-C.sub.4-alkyl, furyl,
furyl-C.sub.1-C.sub.4-alkyl, thienyl, thiazolyl, piperidinyl, or
optionally fluorine-, chlorine-, bromine- or
C.sub.1-C.sub.4-alkyl-substituted phenyl, R.sup.18 represents
hydrogen, in each case optionally fluorine-, chlorine- or
bromine-substituted C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.2-C.sub.6-alkynyl,
C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.4-alkyl,
dioxolanyl-C.sub.1-C.sub.4-alkyl, furyl,
furyl-C.sub.1-C.sub.4-alkyl, thienyl, thiazolyl, piperidinyl, or
optionally fluorine-, chlorine-, bromine- or
C.sub.1-C.sub.4-alkyl-substituted phenyl, or R.sup.17 and R.sup.18
together represent C.sub.3-C.sub.6-alkanediyl or
C.sub.2-C.sub.5-oxaalkanediyl, each of which is optionally
substituted by C.sub.1-C.sub.4-alkyl, phenyl, furyl, a fused
benzene ring or by two substituents which, together with the C atom
to which they are attached, form a 5- or 6-membered carbocycle,
R.sup.19 represents hydrogen, cyano, halogen, or in each case
optionally fluorine-, chlorine- or bromine-substituted
C.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.6-cycloalkyl or phenyl,
R.sup.20 represents hydrogen, in each case optionally hydroxyl-,
cyano-, halogen- or C.sub.1-C.sub.4-alkoxy-substituted
C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-cycloalkyl or
tri(C.sub.1-C.sub.4-alkyl)silyl, R.sup.21 represents hydrogen,
cyano, halogen, or in each case optionally fluorine-, chlorine- or
bromine-substituted C.sub.1-C.sub.4-alkyl,
C.sub.3-C.sub.6-cycloalkyl or phenyl, X.sup.1 represents nitro,
cyano, halogen, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl,
C.sub.1-C.sub.4-alkoxy or C.sub.1-C.sub.4-haloalkoxy, X.sup.2
represents hydrogen, cyano, nitro, halogen, C.sub.1-C.sub.4-alkyl,
C.sub.1-C.sub.4-haloalkyl, C.sub.1-C.sub.4-alkoxy or
C.sub.1-C.sub.4-haloalkoxy, X.sup.3 represents hydrogen, cyano,
nitro, halogen, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl,
C.sub.1-C.sub.4-alkoxy or C.sub.1-C.sub.4-haloalkoxy, or a
compound, of the formula (IId) ##STR00136## or of the formula (IIe)
##STR00137## where t represents a number 0, 1, 2, 3, 4 or 5, v
represents a number 0, 1, 2, 3, 4 or 5, R.sup.22 represents
hydrogen or C.sub.1-C.sub.4-alkyl, R.sup.23 represents hydrogen or
C.sub.1-C.sub.4-alkyl, R.sup.24 represents hydrogen, in each case
optionally cyano-, halogen- or C.sub.1-C.sub.4-alkoxy-substituted
C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.6-alkylthio, C.sub.1-C.sub.6-alkylamino or
di(C.sub.1-C.sub.4-alkyl)amino, or in each case optionally cyano-,
halogen- or C.sub.1-C.sub.4-alkyl-substituted
C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkyloxy,
C.sub.3-C.sub.6-cycloalkylthio or C.sub.3-C.sub.6-cycloalkylamino,
R.sup.25 represents hydrogen, optionally cyano-, hydroxyl-,
halogen- or C.sub.1-C.sub.4-alkoxy-substituted
C.sub.1-C.sub.6-alkyl, in each case optionally cyano- or
halogen-substituted C.sub.3-C.sub.6-alkenyl or
C.sub.3-C.sub.6-alkynyl, or optionally cyano-, halogen- or
C.sub.1-C.sub.4-alkyl-substituted C.sub.3-C.sub.6-cycloalkyl,
R.sup.26 represents hydrogen, optionally cyano-, hydroxyl-,
halogen- or C.sub.1-C.sub.4-alkoxy-substituted
C.sub.1-C.sub.6-alkyl, in each case optionally cyano- or
halogen-substituted C.sub.3-C.sub.6-alkenyl or
C.sub.3-C.sub.6-alkynyl, optionally cyano-, halogen- or
C.sub.1-C.sub.4-alkyl-substituted C.sub.3-C.sub.6-cycloalkyl, or
optionally nitro-, cyano-, halogen-, C.sub.1-C.sub.4-alkyl-,
C.sub.1-C.sub.4-haloalkyl-, C.sub.1-C.sub.4-alkoxy- or
C.sub.1-C.sub.4-haloalkoxy-substituted phenyl, or together with
R.sup.25 represents in each case optionally
C.sub.1-C.sub.4-alkyl-substituted C.sub.2-C.sub.6-alkanediyl or
C.sub.2-C.sub.5-oxaalkanediyl, X.sup.4 represents nitro, cyano,
carboxyl, carbamoyl, formyl, sulfamoyl, hydroxyl, amino, halogen,
C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl,
C.sub.1-C.sub.4-alkoxy or C.sub.1-C.sub.4-haloalkoxy, and X.sup.5
represents nitro, cyano, carboxyl, carbamoyl, formyl, sulfamoyl,
hydroxyl, amino, halogen, C.sub.1-C.sub.4-alkyl,
C.sub.1-C.sub.4-haloalkyl, C.sub.1-C.sub.4-alkoxy or
C.sub.1-C.sub.4-haloalkoxy, or combinations thereof.
8. A composition according to claim 7 in which the crop plant
tolerance promoter compound is selected from the group consisting
of: cloquintocet-mexyl, fenchlorazole-ethyl, isoxadifen-ethyl,
mefenpyr-diethyl, furilazole, fenclorim, cumyluron, dymron,
##STR00138##
9. A composition according to claim 8, in which the crop plant
tolerance promoter compound is cloquintocet-mexyl.
10. A composition according to claim 8, in which the crop plant
tolerance promoter compound is mefenpyr-diethyl.
11. (canceled)
12. A pesticide or herbicide, comprising a compound according to
claim 1.
13. A method for controlling animal pests or unwanted vegetation
comprising contacting pests or their habitat with a compound
according to claim 1.
14. (canceled)
15. A process for preparing pesticides or herbicides, comprising
mixing a compound according to claim 1 with an extender or a
surfactant.
16. A method for controlling unwanted vegetation, comprising
contacting unwanted vegetation with a composition according to
claim 7.
17. (canceled)
18. A method for controlling unwanted vegetation, comprising
contacting plants or their habitat with a compound according to
claim 1 and a crop plant tolerance promoter compound selected from
the group consisting of:
4-dichloroacetyl-1-oxa-4-azaspiro[4.5]decane (AD-67, MON-4660),
1-dichloroacetylhexahydro-3,3,8a-trimethylpyrrolo[1,2-a]pyrimidin-6(2H)-o-
ne (dicyclonon, BAS-145138),
4-dichloroacetyl-3,4-dihydro-3-methyl-2H-1,4-benzoxazine
(benoxacor), 1-methylhexyl 5-chloroquinoline-8-oxyacetate
(cloquintocet-mexyl),
3-(2-chlorobenzyl)-1-(1-methyl-1-phenylethyl)urea (cumyluron),
.alpha.-(cyanomethoximino)phenylacetonitrile (cyometrinil),
2,4-dichlorophenoxyacetic acid (2,4-D),
4-(2,4-dichlorophenoxy)butyric acid (2,4-DB),
1-(1-methyl-1-phenylethyl)-3-(4-methylphenyl)urea (daimuron,
dymron), 3,6-dichloro-2-methoxybenzoic acid (dicamba),
S-1-methyl-1-phenylethyl piperidine-1-thiocarboxylate
(dimepiperate),
2,2-dichloro-N-(2-oxo-2-(2-propenylamino)ethyl)-N-(2-propenyl)acetamide
(DKA-24), 2,2-dichloro-N,N-di-2-propenylacetamide (dichlormid),
4,6-dichloro-2-phenylpyrimidine (fenclorim), ethyl
1-(2,4-dichlorophenyl)-5-trichloromethyl-1H-1,2,4-triazole-3-carboxylate
(fenchlorazole-ethyl), phenylmethyl
2-chloro-4-trifluoromethylthiazole-5-carboxylate (flurazole),
4-chloro-N-(1,3-dioxolan-2-ylmethoxy)-.alpha.-trifluoroacetophenone
oxime (fluxofenim),
3-dichloroacetyl-5-(2-furanyl)-2,2-dimethyloxazolidine (furilazole,
MON-13900), ethyl 4,5-dihydro-5,5-diphenyl-3-isoxazolecarboxylate
(isoxadifen-ethyl), 1-(ethoxycarbonyl)ethyl
3,6-dichloro-2-methoxybenzoate (lactidichlor),
(4-chloro-o-tolyloxy)acetic acid (MCPA),
2-(4-chloro-o-tolyloxy)propionic acid (mecoprop), diethyl
1-(2,4-dichorophenyl)-4,5-dihydro-5-methyl-1H-pyrazole-3,5-dicarboxylate
(mefenpyr-diethyl), 2-dichloromethyl-2-methyl-1,3-dioxolane
(MG-191), 2-propenyl-1-oxa-4-azaspiro[4.5]decane-4-carbodithioate
(MG-838), 1,8-naphthalic anhydride,
.alpha.-(1,3-dioxolan-2-ylmethoximino)phenylacetonitrile
(oxabetrinil),
2,2-dichloro-N-(1,3-dioxolan-2-ylmethyl)-N-(2-propenyl)acetamide
(PPG-1292), 3-dichloroacetyl-2,2-di-methyloxazolidine (R-28725),
3-dichloroacetyl-2,2,5-trimethyloxazolidine (R-29148),
4-(4-chloro-o-tolyl)butyric acid, 4-(4-chlorophenoxy)butyric acid,
diphenylmethoxyacetic acid, methyl diphenylmethoxyacetate, ethyl
diphenylmethoxyacetate, methyl
1-(2-chlorophenyl)-5-phenyl-1H-pyrazole-3-carboxylate, ethyl
1-(2,4-dichlorophenyl)-5-methyl-1H-pyrazole-3-carboxylate, ethyl
1-(2,4-dichlorophenyl)-5-isopropyl-1H-pyrazole-3-carboxylate, ethyl
1-(2,4-dichlorophenyl)-5-(1,1-dimethylethyl)-1H-pyrazole-3-carboxylate,
ethyl 1-(2,4-dichlorophenyl)-5-phenyl-1H-pyrazole-3-carboxylate,
ethyl 5-(2,4-dichlorobenzyl)-2-isoxazoline-3-carboxylate, ethyl
5-phenyl-2-isoxazoline-3-carboxylate, ethyl
5-(4-fluorophenyl)-5-phenyl-2-isoxazoline-3-carboxylate,
1,3-dimethylbut-1-yl 5-chloroquinoline-8-oxyacetate,
4-allyloxybutyl 5-chloroquinoline-8-oxyacetate, 1-allyloxyprop-2-yl
5-chloroquinoline-8-oxyacetate, methyl
5-chloroquinoxaline-8-oxyacetate, ethyl
5-chloroquinoline-8-oxyacetate, allyl
5-chloroquinoxaline-8-oxyacetate, 2-oxoprop-1-yl
5-chloroquinoline-8-oxyacetate, diethyl
5-chloroquinoline-8-oxymalonate, diallyl
5-chloroquinoxaline-8-oxymalonate, diethyl
5-chloroquinoline-8-oxymalonate, 4-carboxychroman-4-ylacetic acid
(AC-304415), 4-chlorophenoxyacetic acid,
3,3'-dimethyl-4-methoxybenzophenone,
1-bromo-4-chloromethylsulfonylbenzene,
1-[4-(N-2-methoxybenzoylsulfamoyl)phenyl]-3-methylurea (also known
as
N-(2-methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide),
1-[4-(N-2-methoxybenzoylsulfamoyl)phenyl]-3,3-dimethylurea,
1-[4-(N-4,5-dimethylbenzoylsulfamoyl)phenyl]-3-methylurea,
1-[4-(N-naphthylsulfamoyl)-phenyl]-3,3-dimethylurea,
N-(2-methoxy-5-methylbenzoyl)-4-(cyclopropylaminocarbonyl)benzenesulfonam-
ide, separately in close temporal succession.
19. A method for preparing 2,6-diethyl-4-methylphenylacetic acid,
comprising reacting 2,6-diethyl-2-methylbromobenzene with
tert-butyl acetate, optionally in the presence of a base, a
phosphine ligand, a palladium compound and a diluent, and then
reacting with an acid.
20. A process for preparing 2,6-diethyl-4-methylphenylacetic acid,
comprising reacting 2,6-diethyl-4-methylphenylmalononitrile with an
acid, optionally in the presence of a diluent.
Description
[0001] The invention relates to novel
2,6-diethyl-4-methylphenyl-substituted tetramic acid derivatives,
to a plurality of processes for their preparation and to their use
as pesticides and/or herbicides. Moreover, the invention relates to
novel selective herbicidal active compound combinations comprising,
firstly, the 2,6-diethyl-4-methylphenyl-substituted tetramic acid
derivatives and, secondly, a crop plant tolerance promoter
compound, which combinations can be used with particularly good
results for the selective control of weeds in various crops of
useful plants.
[0002] Pharmaceutical properties of 3-acylpyrrolidine-2,4-diones
are described in the prior art (S. Suzuki et al. Chem. Pharm. Bull.
15 1120 (1967)). Furthermore, R. Schmierer and H. Mildenberger
(Liebigs Ann. Chem. 1985, 1095) synthesize
N-phenylpyrrolidine-2,4-diones. A biological activity of these
compounds has not been described.
[0003] EP-A-0 262 399 and GB-A-2 266 888 disclose compounds of a
similar structure (3-arylpyrrolidine-2,4-diones); however, a
herbicidal, insecticidal or acaricidal action of these compounds is
not known. Known to have a herbicidal, insecticidal or acaricidal
action are unsubstituted, bicyclic 3-arylpyrrolidine-2,4-dione
derivatives (EP-A-355 599 and EP-A-415 211), and also substituted
monocyclic 3-arylpyrrolidine-2,4-dione derivatives (EP-A-377 893
and EP-A-442 077).
[0004] Also known are polycyclic 3-arylpyrrolidine-2,4-dione
derivatives (EP-A-442 073), and also 1H-arylpyrrolidine dione
derivatives (EP-A-456 063, EP-A-521 334, EP-A-596 298, EP-A-613
884, EP-A-613 885, WO 94/01 997, WO 95/26954, WO 95/20 572, EP-A 0
668 267, WO 96/25 395, WO 96 35 664, WO 97/01 535, WO 97/02 243, WO
97/36 868, WO 97/43275, WO/98/05638, WO 98/06721, WO 98/25928, WO
99/16748, WO 99/24437, WO 99/43649, WO 99/48869, WO 99/55673, WO
01/09092, WO 01/17 972, WO 01/23354, WO 01/74770, WO 03/013249, WO
2004/007448, DE-A-10 239 479, WO 04/065336, WO 04/080962, WO
04/111042, WO 05/044791, WO 05/044796, WO 05/048710, WO 05/049569,
DE-A-04 001 433).
[0005] However, the efficacy and activity spectrum of these
compounds, in particular at low application rates and
concentrations, are not always satisfactory. Furthermore, the
compatibility of these compounds with crops is not always
sufficient.
[0006] This invention now provides novel compounds of the formula
(I)
##STR00002##
in which [0007] A represents hydrogen, represents in each case
optionally halogen-substituted alkyl, alkenyl, alkoxyalkyl or
alkylthioalkyl or represents optionally substituted cycloalkyl,
[0008] B represents hydrogen, alkyl or alkoxyalkyl, or [0009] A and
B together with the carbon atom to which they are attached
represent a saturated or unsaturated C.sub.3-C.sub.8-ring which
optionally contains at least one heteroatom and which is optionally
substituted and [0010] D represents hydrogen, [0011] or [0012] A
represents hydrogen or alkyl, [0013] B represents hydrogen and
[0014] D represents an optionally substituted radical from the
group consisting of alkyl, alkenyl, alkynyl, alkoxyalkyl,
alkylthioalkyl or optionally cycloalkyl, or [0015] A and D together
with the atoms to which they are attached represent a saturated or
unsaturated cycle which optionally contains at least one oxygen or
sulfur atom in the A,D moiety or which is optionally substituted by
alkyl, alkoxy or haloalkyl and [0016] G represents one of the
groups
[0016] ##STR00003## [0017] in which [0018] E represents a metal ion
equivalent or an ammonium ion, [0019] L represents oxygen or
sulfur, [0020] M represents oxygen or sulfur, [0021] R.sup.1
represents in each case optionally substituted primary or secondary
alkyl, alkenyl, alkoxy-alkyl, alkylthioalkyl or polyalkoxyalkyl or
represents in each case optionally halogen-, alkyl- or
alkoxy-substituted cycloalkyl or heterocyclyl or represents in each
case optionally substituted phenyl or hetaryl, [0022] R.sup.2
represents in each case optionally halogen-substituted alkyl,
alkenyl, alkoxyalkyl or polyalkoxyalkyl or represents in each case
optionally substituted cycloalkyl, phenyl or benzyl, [0023]
R.sup.3, R.sup.4 and R.sup.5 independently of one another represent
in each case optionally halogen-substituted alkyl, alkoxy,
alkylamino, dialkylamino, alkylthio, alkenylthio or cycloalkylthio
or represent in each case optionally substituted phenyl, benzyl,
phenoxy or phenylthio, [0024] R.sup.6 and R.sup.7 independently of
one another represent hydrogen, represent in each case optionally
halogen-substituted alkyl, cycloalkyl, alkenyl, alkoxy,
alkoxyalkyl, represent in each case optionally substituted phenyl
or benzyl or together with the N atom to which they are attached
form an optionally substituted cycle which optionally contains
oxygen or sulfur.
[0025] Depending inter alia on the nature of the substitutents, the
compounds of the formula (I) can be present as geometrical and/or
optical isomers or isomer mixtures of varying composition which, if
appropriate, may be separated in a customary manner. The present
invention provides both the pure isomers and the isomer mixtures,
their preparation and use, and compositions comprising them.
However, for the sake of simplicity, hereinbelow only compounds of
the formula (I) are referred to, although what is meant are both
the pure compounds and, if appropriate, also mixtures having
varying proportions of isomeric compounds.
[0026] Including the meanings (b), (c), (d), (e), (f) and (g) of
group G, the following principal structures (I-b) to (I-g)
result:
##STR00004## ##STR00005##
in which A, B, D, E, L, M, R.sup.1, R.sup.2, R.sup.3, R.sup.4,
R.sup.5, R.sup.6 and R.sup.7 are as defined above.
[0027] Furthermore, it has been found that the novel compounds of
the formula (I) are obtained by one of the processes described
below: [0028] (A) compounds of the formula (I-b) shown above in
which A, B, D and R.sup.1 are as defined above are obtained when
compounds of the formula (I-a)
[0028] ##STR00006## [0029] in which [0030] A, B and D are as
defined above [0031] are reacted [0032] .alpha.) with acid halides
of the formula (II)
[0032] ##STR00007## [0033] in which [0034] R.sup.1 is as defined
above and [0035] Hal represents halogen (in particular chlorine or
bromine) [0036] or [0037] .beta.) with carboxylic anhydrides of the
formula (II)
[0037] R.sup.1--CO--O--CO--R.sup.1 (III) [0038] in which [0039]
R.sup.1 is as defined above, [0040] if appropriate in the presence
of a diluent and if appropriate in the presence of an acid binder.
[0041] (C) Compounds of the formula (I-c) shown above in which A,
B, D, R.sup.2 and M are as defined above and L represents oxygen
are obtained when compounds of the formula (I-a) shown above in
which A, B and D are as defined above are in each case reacted
[0042] with chloroformic esters or chloroformic thioesters of the
formula (IV)
[0042] R.sup.2-M-CO--Cl (IV) [0043] in which [0044] R.sup.2 and M
are as defined above, [0045] if appropriate in the presence of a
diluent and if appropriate in the presence of an acid binder.
[0046] (D) Compounds of the formula (I-c) shown above in which A,
B, D, R.sup.2 and M are as defined above and L represents sulfur
are obtained when compounds of the formula (I-a) shown above in
which A, B and D are as defined above are in each case [0047]
.alpha.) reacted with chloromonothioformic esters or
chlorodithioformic esters of the formula (V)
[0047] ##STR00008## [0048] in which [0049] M and R.sup.2 are as
defined above, [0050] if appropriate in the presence of a diluent
and if appropriate in the presence of an acid binder, [0051] or
[0052] .beta.) reacted with carbon disulfide and then with
compounds of the formula (VI)
[0052] R.sup.2--Hal (VI) [0053] in which [0054] R.sup.2 is as
defined above and [0055] Hal represents chlorine, bromine or
iodine, [0056] if appropriate in the presence of a diluent and if
appropriate in the presence of a base. [0057] (E) Compounds of the
formula (I-d) shown above in which A, B, D and R.sup.3 are as
defined above are obtained when compounds of the formula (I-a)
shown above in which A, B and D are as defined above are in each
case reacted [0058] with sulfonyl chlorides of the formula
(VII)
[0058] R.sup.3--SO.sub.2--Cl (VII) [0059] in which [0060] R.sup.3
is as defined above, [0061] if appropriate in the presence of a
diluent and if appropriate in the presence of an acid binder.
[0062] (F) Compounds of the formula (I-e) shown above in which A,
B, D, L, R.sup.4 and R.sup.5 are as defined above are obtained when
compounds of the formula (I-a) shown above in which A, B and D are
as defined above are in each case reacted [0063] with phosphorus
compounds of the formula (VIII)
[0063] ##STR00009## [0064] in which [0065] L, R.sup.4 and R.sup.5
are as defined above and [0066] Hal represents halogen (in
particular chlorine or bromine), [0067] if appropriate in the
presence of a diluent and if appropriate in the presence of an acid
binder. [0068] (G) Compounds of the formula (I-f) shown above in
which A, B, D and E are as defined above are obtained when
compounds of the formulae (I-a) in which A, B and D are as defined
above are in each case reacted [0069] with metal compounds or
amines of the formulae (IX) or (X)
[0069] ##STR00010## [0070] in which [0071] Me represents a mono- or
divalent metal (preferably an alkali metal or alkaline earth metal,
such as lithium, sodium, potassium, magnesium or calcium), [0072] t
represents the number 1 or 2 and [0073] R.sup.10, R.sup.11,
R.sup.12 independently of one another represent hydrogen or alkyl
(preferably C.sub.1-C.sub.8-alkyl), [0074] if appropriate in the
presence of a diluent. [0075] (H) Compounds of the formula (I-g)
shown above in which A, B, D, L, R.sup.6 and R.sup.7 are as defined
above are obtained when compounds of the formula (I-a) shown above
in which A, B and D are as defined above are in each case [0076]
.alpha.) reacted with isocyanates or isothiocyanates of the formula
(XI)
[0076] R.sup.6--N.dbd.C=L (XI) [0077] in which [0078] R.sup.6 and L
are as defined above, [0079] if appropriate in the presence of a
diluent and if appropriate in the presence of a catalyst, or [0080]
.beta.) reacted with carbamoyl chlorides or thiocarbamoyl chlorides
of the formula (XII)
[0080] ##STR00011## [0081] in which [0082] L, R.sup.6 and R.sup.7
are as defined above, [0083] if appropriate in the presence of a
diluent and if appropriate in the presence of an acid binder.
[0084] Furthermore, it has been found that the novel compounds of
the formula (I) have very good activity as pesticides, preferably
as insecticides and/or acaricides, and/or as herbicides.
[0085] Surprisingly, it has now been found that certain substituted
cyclic ketoenols, when employed together with the crop plant
tolerance promoter compounds (safeners/antidotes) described later
on, are extremely good at preventing damage to the crop plants and
can be used with particular advantage as broad-spectrum combination
products for the selective control of unwanted plants in crops of
useful plants, such as, for example, in cereals, but also in maize,
soybeans and rice.
[0086] The invention also provides selective herbidical
compositions comprising an effective amount of an active compound
combination comprising, as components, [0087] a') at least one
substituted cyclic ketoenol of the formula (I) in which A, B, D and
G are as defined above or [0088] b') at least one substituted
cyclic ketoenol of the formula (I-a)
[0088] ##STR00012## [0089] in which [0090] A represents hydrogen,
C.sub.2-C.sub.10-alkyl, C.sub.1-C.sub.6-haloalkyl, represents in
each case optionally halogen-substituted alkenyl, alkoxyalkyl or
alkylthioalkyl or represents optionally substituted cycloalkyl,
[0091] B represents hydrogen, alkyl or alkoxyalkyl, or [0092] A and
B together with the carbon atom to which they are attached
represent a saturated or unsaturated C.sub.3-C.sub.8-ring which is
substituted by alkyl, alkoxy or haloalkyl or represent a
C.sub.5-C.sub.8-ring which contains at least one heteroatom and
which is optionally substituted, and [0093] D represents hydrogen
or [0094] A represents hydrogen or alkyl, [0095] B represents
hydrogen and [0096] D represents an optionally substituted radical
from the group consisting of C.sub.2-C.sub.10-alkyl, alkenyl,
alkynyl, alkoxyalkyl, alkylthioalkyl or optionally substituted
cycloalkyl, or [0097] A and D together with the atoms to which they
are attached represent a saturated or unsaturated cycle which
optionally contains at least one oxygen or sulfur atom in the
A,D-moiety or which is optionally substituted by alkyl, alkoxy or
haloalkyl, and [0098] (c') at least one crop plant tolerance
promoter compound from the following group of compounds:
4-dichloroacetyl-1-oxa-4-azaspiro[4.5]decane (AD-67, MON-4660),
1-dichloroacetylhexahydro-3,3,8a-trimethylpyrrolo[1,2-a]pyrimidin-6(2H)-o-
ne (dicyclonon, BAS-145138),
4-dichloroacetyl-3,4-dihydro-3-methyl-2H-1,4-benzoxazine
(benoxacor), 1-methylhexyl 5-chloroquinoline-8-oxy-acetate
(cloquintocet-mexyl--cf. also related compounds in EP-A-86750,
EP-A-94349, EP-A-191736, EP-A-492366),
3-(2-chlorobenzyl)-1-(1-methyl-1-phenylethyl)urea (cumyluron),
.alpha.-(cyanomethoximino)phenylacetonitrile (cyometrinil),
2,4-dichlorophenoxyacetic acid (2,4-D),
4-(2,4-dichlorophenoxy)butyric acid (2,4-DB),
1-(1-methyl-1-phenylethyl)-3-(4-methylphenyl)urea (daimuron,
dymron), 3,6-dichloro-2-methoxybenzoic acid (dicamba),
S-1-methyl-1-phenylethyl piperidine-1-thiocarboxylate
(dimepiperate),
2,2-dichloro-N-(2-oxo-2-(2-propenylamino)ethyl)-N-(2-propenyl)acetamide
(DKA-24), 2,2-dichloro-N,N-di-2-propenylacetamide (dichlormid),
4,6-dichloro-2-phenylpyrimidine (fenclorim), ethyl
1-(2,4-dichlorophenyl)-5-trichloromethyl-1H-1,2,4-triazole-3-carboxylate
(fenchlorazole-ethyl--cf. also related compounds in EP-A-174562 and
EP-A-346620), phenylmethyl
2-chloro-4-trifluoromethylthiazole-5-carboxylate (flurazole),
4-chloro-N-(1,3-dioxolan-2-ylmethoxy)-.alpha.-trifluoroacetophenone
oxime (fluxofenim),
3-dichloro-acetyl-5-(2-furanyl)-2,2-dimethyloxazolidine
(furilazole, MON-13900), ethyl
4,5-dihydro-5,5-diphenyl-3-isoxazolecarboxylate
(isoxadifen-ethyl--cf. also related compounds in WO-A-95/07897),
1-(ethoxycarbonyl)ethyl 3,6-dichloro-2-methoxybenzoate
(lactidichlor), (4-chloro-o-tolyloxy)acetic acid (MCPA),
2-(4-chloro-o-tolyloxy)propionic acid (mecoprop), diethyl
1-(2,4-dichorophenyl)-4,5-dihydro-5-methyl-1H-pyrazole-3,5-dicarboxylate
(mefenpyr-diethyl--cf. also related compounds in WO-A-91/07874),
2-dichloromethyl-2-methyl-1,3-dioxolane (MG-191),
2-propenyl-1-oxa-4-azaspiro[4.5]decane-4-carbodithioate (MG-838),
1,8-naphthalic anhydride,
.alpha.-(1,3-dioxolan-2-ylmethoximino)phenylacetonitrile
(oxabetrinil),
2,2-dichloro-N-(1,3-dioxolan-2-ylmethyl)-N-(2-propenyl)acetamide
(PPG-1292), 3-dichloroacetyl-2,2-dimethyloxazolidine (R-28725),
3-dichloroacetyl-2,2,5-trimethyloxazolidine (R-29148),
4-(4-chloro-o-tolyl)butyric acid, 4-(4-chlorophenoxy)butyric acid,
diphenylmethoxyacetic acid, methyl diphenylmethoxyacetate, ethyl
diphenylmethoxyacetate, methyl
1-(2-chlorophenyl)-5-phenyl-1H-pyrazole-3-carboxylate, ethyl
1-(2,4-dichlorophenyl)-5-methyl-1H-pyrazole-3-carboxylate, ethyl
1-(2,4-dichlorophenyl)-5-isopropyl-1H-pyrazole-3-carboxylate, ethyl
1-(2,4-dichlorophenyl)-5-(1,1-dimethylethyl)-1H-pyrazole-3-carboxylate,
ethyl 1-(2,4-dichlorophenyl)-5-phenyl-1H-pyrazole-3-carboxylate
(cf. also related compounds in EP-A-269806 and EP-A-333131), ethyl
5-(2,4-dichlorobenzyl)-2-isoxazoline-3-carboxylate, ethyl
5-phenyl-2-isoxazoline-3-carboxylate, ethyl
5-(4-fluorophenyl)-5-phenyl-2-isoxazoline-3-carboxylate (cf. also
related compounds in WO-A-91/08202), 1,3-dimethylbut-1-yl
5-chloroquinoline-8-oxyacetate, 4-allyloxybutyl
5-chloroquinoline-8-oxyacetate, 1-allyloxyprop-2-yl
5-chloroquinoline-8-oxyacetate, methyl
5-chloroquinoxaline-8-oxyacetate, ethyl
5-chloroquinoline-8-oxyacetate, allyl
5-chloroquinoxaline-8-oxyacetate, 2-oxoprop-1-yl
5-chloroquinoline-8-oxyacetate, diethyl
5-chloroquinoline-8-oxymalonate, diallyl
5-chloroquinoxaline-8-oxymalonate, diethyl
5-chloroquinoline-8-oxymalonate (cf. also related compounds in
EP-A-582198), 4-carboxychroman-4-ylacetic acid (AC-304415, cf.
EP-A-613618), 4-chlorophenoxyacetic acid,
3,3'-dimethyl-4-methoxybenzophenone,
1-bromo-4-chloromethylsulfonylbenzene,
1-[4-(N-2-methoxybenzoylsulfamoyl)-phenyl]-3-methylurea (also known
as
N-(2-methoxybenzoyl)-4-[(methylaminocarbonyl)-amino]benzenesulfonamide),
1-[4-(N-2-methoxybenzoylsulfamoyl)phenyl]-3,3-dimethylurea,
1-[4-(N-4,5-dimethylbenzoylsulfamoyl)phenyl]-3-methylurea,
1-[4-(N-naphthylsulfamoyl)phenyl]-3,3-dimethylurea,
N-(2-methoxy-5-methylbenzoyl)-4-(cyclopropylaminocarbonyl)benzenesulfonam-
ide, and/or one of the following compounds, defined by general
formulae, of the general formula (IIa)
##STR00013##
[0098] or of the general formula (IIb)
##STR00014##
or of the formula (IIc)
##STR00015##
where [0099] m represents a number 0, 1, 2, 3, 4 or 5, [0100]
A.sup.1 represents one of the divalent heterocyclic groupings shown
below
[0100] ##STR00016## [0101] n represents a number 0, 1, 2, 3, 4 or
5, [0102] A.sup.2 represents optionally C.sub.1-C.sub.4-alkyl-
and/or C.sub.1-C.sub.4-alkoxy-carbonyl- and/or
C.sub.1-C.sub.4-alkenyloxy-carbonyl-substituted alkanediyl having 1
or 2 carbon atoms, [0103] R.sup.14 represents hydroxyl, mercapto,
amino, C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-alkylthio,
C.sub.1-C.sub.6-alkylamino or di(C.sub.1-C.sub.4-alkyl)amino,
[0104] R.sup.15 represents hydroxyl, mercapto, amino,
C.sub.1-C.sub.7-alkoxy, C.sub.1-C.sub.6-alkenyloxy,
C.sub.1-C.sub.6-alkenyloxy-C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.6-alkylthio, C.sub.1-C.sub.6-alkylamino or
di(C.sub.1-C.sub.4-alkyl)amino, [0105] R.sup.16 represents in each
case optionally fluorine-, chlorine- and/or bromine-substituted
C.sub.1-C.sub.4-alkyl, [0106] R.sup.17 represents hydrogen, in each
case optionally fluorine-, chlorine- and/or bromine-substituted
C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl or
C.sub.2-C.sub.6-alkynyl,
C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.4-alkyl,
dioxolanyl-C.sub.1-C.sub.4-alkyl, furyl,
furyl-C.sub.1-C.sub.4-alkyl, thienyl, thiazolyl, piperidinyl, or
optionally fluorine-, chlorine- and/or bromine- or
C.sub.1-C.sub.4-alkyl-substituted phenyl, [0107] R.sup.18
represents hydrogen, in each case optionally fluorine-, chlorine-
and/or bromine-substituted C.sub.1-C.sub.6-alkyl,
C.sub.2-C.sub.6-alkenyl or C.sub.2-C.sub.6-alkynyl,
C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.4-alkyl,
dioxolanyl-C.sub.1-C.sub.4-alkyl, furyl,
furyl-C.sub.1-C.sub.4-alkyl, thienyl, thiazolyl, piperidinyl, or
optionally fluorine-, chlorine- and/or bromine- or
C.sub.1-C.sub.4-alkyl-substituted phenyl, [0108] R.sup.17 and
R.sup.18 also together represent C.sub.3-C.sub.6-alkanediyl or
C.sub.2-C.sub.5-oxaalkanediyl, each of which is optionally
substituted by C.sub.1-C.sub.4-alkyl, phenyl, furyl, a fused
benzene ring or by two substituents which, together with the C atom
to which they are attached, form a 5- or 6-membered carboxycle,
[0109] R.sup.19 represents hydrogen, cyano, halogen, or represents
in each case optionally fluorine-, chlorine- and/or
bromine-substituted C.sub.1-C.sub.4-alkyl,
C.sub.3-C.sub.6-cycloalkyl or phenyl, [0110] R.sup.20 represents
hydrogen, optionally hydroxyl-, cyano-, halogen- or
C.sub.1-C.sub.4-alkoxy-substituted C.sub.1-C.sub.6-alkyl,
C.sub.3-C.sub.6-cycloalkyl or tri(C.sub.1-C.sub.4-alkyl)silyl,
[0111] R.sup.21 represents hydrogen, cyano, halogen, or represents
in each case optionally fluorine-, chlorine- and/or
bromine-substituted C.sub.1-C.sub.4-alkyl,
C.sub.3-C.sub.6-cycloalkyl or phenyl, [0112] X.sup.1 represents
nitro, cyano, halogen, C.sub.1-C.sub.4-alkyl,
C.sub.1-C.sub.4-haloalkyl, C.sub.1-C.sub.4-alkoxy or
C.sub.1-C.sub.4-haloalkoxy, [0113] X.sup.2 represents hydrogen,
cyano, nitro, halogen, C.sub.1-C.sub.4-alkyl,
C.sub.1-C.sub.4-haloalkyl, C.sub.1-C.sub.4-alkoxy or
C.sub.1-C.sub.4-haloalkoxy, [0114] X.sup.3 represents hydrogen,
cyano, nitro, halogen, C.sub.1-C.sub.4-alkyl,
C.sub.1-C.sub.4-haloalkyl, C.sub.1-C.sub.4-alkoxy or
C.sub.1-C.sub.4-haloalkoxy, and/or the following compounds, defined
by general formulae, of the general formula (IId)
##STR00017##
[0114] or of the general formula (IIe)
##STR00018##
where [0115] t represents a number 0, 1, 2, 3, 4 or 5, [0116] v
represents a number 0, 1, 2, 3, 4 or 5, [0117] R.sup.22 represents
hydrogen or C.sub.1-C.sub.4-alkyl, [0118] R.sup.23 represents
hydrogen or C.sub.1-C.sub.4-alkyl, [0119] R.sup.24 represents
hydrogen, in each case optionally cyano-, halogen- or
C.sub.1-C.sub.4-alkoxy-substituted C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-alkylthio,
C.sub.1-C.sub.6-alkylamino or di(C.sub.1-C.sub.4-alkyl)amino, or in
each case optionally cyano-, halogen- or
C.sub.1-C.sub.4-alkyl-substituted C.sub.3-C.sub.6-cycloalkyl,
C.sub.3-C.sub.6-cycloalkyloxy, C.sub.3-C.sub.6-cycloalkylthio or
C.sub.3-C.sub.6-cycloalkylamino, [0120] R.sup.25 represents
hydrogen, optionally cyano-, hydroxyl-, halogen- or
C.sub.1-C.sub.4-alkoxy-substituted C.sub.1-C.sub.6-alkyl, in each
case optionally cyano- or halogen-substituted
C.sub.3-C.sub.6-alkenyl or C.sub.3-C.sub.6-alkynyl, or optionally
cyano-, halogen- or C.sub.1-C.sub.4-alkyl-substituted
C.sub.3-C.sub.6-cycloalkyl, [0121] R.sup.26 represents hydrogen,
optionally cyano-, hydroxyl-, halogen- or
C.sub.1-C.sub.4-alkoxy-substituted C.sub.1-C.sub.6-alkyl, in each
case optionally cyano- or halogen-substituted
C.sub.3-C.sub.6-alkenyl or C.sub.3-C.sub.6-alkynyl, optionally
cyano-, halogen- or C.sub.1-C.sub.4-alkyl-substituted
C.sub.3-C.sub.6-cycloalkyl, or optionally nitro-, cyano-, halogen-,
C.sub.1-C.sub.4-alkyl-, C.sub.1-C.sub.4-haloalkyl-,
C.sub.1-C.sub.4-alkoxy- or C.sub.1-C.sub.4-haloalkoxy-substituted
phenyl, or together with R.sup.25 represents in each case
optionally C.sub.1-C.sub.4-alkyl-substituted
C.sub.2-C.sub.6-alkanediyl or C.sub.2-C.sub.5-oxaalkanediyl, [0122]
X.sup.4 represents nitro, cyano, carboxyl, carbamoyl, formyl,
sulfamoyl, hydroxyl, amino, halogen, C.sub.1-C.sub.4-alkyl,
C.sub.1-C.sub.4-haloalkyl, C.sub.1-C.sub.4-alkoxy or
C.sub.1-C.sub.4-haloalkoxy, and [0123] X.sup.5 represents nitro,
cyano, carboxyl, carbamoyl, formyl, sulfamoyl, hydroxyl, amino,
halogen, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl,
C.sub.1-C.sub.4-alkoxy or C.sub.1-C.sub.4-haloalkoxy.
[0124] The formula (I) provides a general definition of the
compounds according to the invention. Preferred substituents or
ranges of the radicals listed in the formulae given above and below
are illustrated below: [0125] A preferably represents hydrogen,
represents C.sub.1-C.sub.8-alkyl, C.sub.2-C.sub.8-alkenyl,
C.sub.2-C.sub.8-alkoxy-C.sub.1-C.sub.4-alkyl or
C.sub.1-C.sub.6-alkylthio-C.sub.1-C.sub.4-alkyl, each of which is
optionally mono- to trisubstituted by halogen, represents
C.sub.3-C.sub.8-cycloalkyl which is optionally mono- to
trisubstituted by halogen, C.sub.1-C.sub.6-alkyl or
C.sub.1-C.sub.6-alkoxy, [0126] B preferably represents hydrogen,
C.sub.1-C.sub.6-alkyl or
C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.2-alkyl or [0127] A, B and the
carbon atom to which they are attached preferably represent
saturated C.sub.3-C.sub.8-cycloalkyl or unsaturated
C.sub.5-C.sub.8-cycloalkyl in which optionally one methylene group
is replaced by oxygen or sulfur and which is optionally substituted
by C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.4-haloalkyl or
C.sub.1-C.sub.6-alkoxy, and [0128] D preferably represents
hydrogen, [0129] or [0130] A preferably represents hydrogen or
C.sub.1-C.sub.8-alkyl, [0131] B preferably represents hydrogen and
[0132] D preferably represents C.sub.1-C.sub.8-alkyl,
C.sub.1-C.sub.8-alkenyl,
C.sub.1-C.sub.6-alkoxy-C.sub.2-C.sub.4-alkyl or
C.sub.1-C.sub.6-alkylthio-C.sub.2-C.sub.4-alkyl, each of which is
optionally mono- to pentasubstituted by halogen, represents
C.sub.3-C.sub.8-cycloalkyl which is optionally mono- to
trisubstituted by halogen, C.sub.1-C.sub.4-alkyl,
C.sub.1-C.sub.4-alkoxy or C.sub.1-C.sub.2-haloalkyl, or [0133] A
and D together preferably represent a C.sub.3-C.sub.6-alkanediyl or
C.sub.3-C.sub.6-alkenediyl group in which in each case optionally
one methylene group is replaced by oxygen or sulfur and which is in
each case mono- to disubstituted by C.sub.1-C.sub.4-alkyl,
C.sub.1-C.sub.4-alkoxy or C.sub.1-C.sub.4-haloalkyl or by a further
C.sub.3-C.sub.6-alkanediyl, C.sub.3-C.sub.6-alkenediyl or
C.sub.4-C.sub.6-alkanedienediyl group which forms a fused-on ring,
[0134] G preferably represents one of the groups
[0134] ##STR00019## [0135] in which [0136] E represents a metal ion
equivalent or an ammonium ion, [0137] L represents oxygen or sulfur
and [0138] M represents oxygen or sulfur, [0139] R.sup.1 preferably
represents primary or secondary C.sub.1-C.sub.20-alkyl,
C.sub.2-C.sub.20-alkenyl,
C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-alkylthio-C.sub.1-C.sub.6-alkyl or
poly-C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.4-alkyl, each of which is
optionally mono- to heptasubstituted by halogen, mono- to
disubstituted by cyano, monosubstituted by COR.sup.13,
C.dbd.N--OR.sup.13, CO.sub.2R.sup.13 or
##STR00020##
[0139] or represents C.sub.3-C.sub.8-cycloalkyl which is optionally
mono- to trisubstituted by halogen, C.sub.1-C.sub.4-alkyl or
C.sub.1-C.sub.4-alkoxy and in which optionally one or two not
directly adjacent methylene groups are replaced by oxygen and/or
sulfur, [0140] represents phenyl, phenyl-C.sub.1-C.sub.2-alkyl or
phenyl-C.sub.1-C.sub.2-alkenyl, each of which is optionally mono-
to trisubstituted by halogen, cyano, nitro, C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-haloalkyl,
C.sub.1-C.sub.6-haloalkoxy, C.sub.1-C.sub.6-alkylthio,
C.sub.1-C.sub.6-alkylsulfinyl or C.sub.1-C.sub.6-alkylsulfonyl,
[0141] represents 5- or 6-membered hetaryl which is optionally
mono- to disubstituted by halogen or C.sub.1-C.sub.6-alkyl and
which has one or two heteroatoms from the group consisting of
oxygen, sulfur and nitrogen, [0142] R.sup.2 preferably represents
C.sub.1-C.sub.20-alkyl, C.sub.2-C.sub.20-alkenyl,
C.sub.1-C.sub.6-alkoxy-C.sub.2-C.sub.6-alkyl or
poly-C.sub.1-C.sub.6-alkoxy-C.sub.2-C.sub.6-alkyl, each of which is
optionally mono- to trisubstituted by halogen, [0143] represents
C.sub.3-C.sub.8-cycloalkyl which is optionally mono- to
disubstituted by halogen, C.sub.1-C.sub.6-alkyl or
C.sub.1-C.sub.6-alkoxy or [0144] represents phenyl or benzyl, each
of which is optionally mono- to trisubstituted by halogen, cyano,
nitro, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.6-haloalkyl or C.sub.1-C.sub.6-haloalkoxy, [0145]
R.sup.3 preferably represents C.sub.1-C.sub.8-alkyl which is
optionally mono- to polysubstituted by halogen or represents phenyl
or benzyl, each of which is optionally mono- to disubstituted by
halogen, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.4-haloalkyl, C.sub.1-C.sub.4-haloalkoxy, cyano or
nitro, [0146] R.sup.4 and R.sup.5 independently of one another
preferably represent C.sub.1-C.sub.8-alkyl, C.sub.1-C.sub.8-alkoxy,
C.sub.1-C.sub.8-alkyl-amino, di(C.sub.1-C.sub.8-alkyl)amino,
C.sub.1-C.sub.8-alkylthio or C.sub.2-C.sub.8-alkenylthio, each of
which is optionally mono- to trisubstituted by halogen, or
represent phenyl, phenoxy or phenylthio, each of which is
optionally mono- to trisubstituted by halogen, nitro, cyano,
C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.4-haloalkoxy,
C.sub.1-C.sub.4-alkylthio, C.sub.1-C.sub.4-haloalkylthio,
C.sub.1-C.sub.4-alkyl or C.sub.1-C.sub.4-haloalkyl, [0147] R.sup.6
and R.sup.7 independently of one another preferably represent
hydrogen, represent C.sub.1-C.sub.8-alkyl,
C.sub.3-C.sub.8-cycloalkyl, C.sub.1-C.sub.8-alkoxy,
C.sub.3-C.sub.8-alkenyl or
C.sub.1-C.sub.8-alkoxy-C.sub.2-C.sub.8-alkyl, each of which is
optionally mono- to trisubstituted by halogen, represent phenyl or
benzyl, each of which is optionally mono- to trisubstituted by
halogen, C.sub.1-C.sub.8-alkyl, C.sub.1-C.sub.8-haloalkyl or
C.sub.1-C.sub.8-alkoxy, or together represent a
C.sub.3-C.sub.6-alkylene radical which is optionally mono- to
disubstituted by C.sub.1-C.sub.4-alkyl in which optionally one
methylene group is replaced by oxygen or sulfur, [0148] R.sup.13
preferably represents C.sub.1-C.sub.6-alkyl,
C.sub.3-C.sub.6-alkenyl, C.sub.3-C.sub.6-alkynyl or
C.sub.1-C.sub.4-alkoxy-C.sub.2-C.sub.4-alkyl, each of which is
optionally mono- to trisubstituted by halogen, or represents
C.sub.3-C.sub.6-cycloalkyl which is optionally mono- to
disubstituted by halogen, C.sub.1-C.sub.2-alkyl or
C.sub.1-C.sub.2-alkoxy and in which optionally one or two not
directly adjacent methylene groups are replaced by oxygen or
represents phenyl or phenyl-C.sub.1-C.sub.2-alkyl, each of which is
optionally mono- to disubstituted by fluorine, chlorine, bromine,
C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy,
C.sub.1-C.sub.2-haloalkyl, C.sub.1-C.sub.2-haloalkoxy, cyano or
nitro, [0149] R.sup.13' preferably represents hydrogen,
C.sub.1-C.sub.6-alkyl or C.sub.3-C.sub.6-alkenyl.
[0150] In the radical definitions mentioned as being preferred,
halogen represents fluorine, chlorine, bromine and iodine, in
particular fluorine, chlorine and bromine. [0151] A particularly
preferably represents hydrogen, represents C.sub.1-C.sub.6-alkyl,
C.sub.2-C.sub.6-alkenyl,
C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.3-alkyl or
C.sub.1-C.sub.4-alkylthio-C.sub.1-C.sub.3-alkyl, each of which is
optionally mono- to trisubstituted by fluorine or chlorine, or
represents C.sub.3-C.sub.6-cycloalkyl which is optionally mono- to
disubstituted by fluorine, chlorine, C.sub.1-C.sub.2-alkyl or
C.sub.1-C.sub.2-alkoxy, [0152] B particularly preferably represents
hydryogen, C.sub.1-C.sub.4-alkyl or
C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.2-alkyl, or [0153] A, B and
the carbon atom to which they are attached particularly preferably
represent saturated C.sub.3-C.sub.7-cycloalkyl in which optionally
one methylene group is replaced by oxygen and which is optionally
mono- to disubstituted by C.sub.1-C.sub.4-alkyl,
C.sub.1-C.sub.2-haloalkyl or C.sub.1-C.sub.4-alkoxy, and [0154] D
particularly preferably represents hydrogen, or [0155] A
particularly preferably represents hydrogen or
C.sub.1-C.sub.6-alkyl, [0156] B particularly preferably represents
hydrogen and [0157] D particularly preferably represents
C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-alkenyl,
C.sub.1-C.sub.4-alkoxy-C.sub.2-C.sub.3-alkyl or
C.sub.1-C.sub.4-alkylthio-C.sub.2-C.sub.3-alkyl, each of which is
optionally mono- to trisubstituted by fluorine or chlorine,
represents C.sub.3-C.sub.6-cycloalkyl which is optionally mono- to
disubstituted by fluorine, chlorine, C.sub.1-C.sub.2-alkyl,
C.sub.1-C.sub.2-alkoxy or trifluoromethyl, or [0158] A and D
together particularly preferably represent a
C.sub.3-C.sub.5-alkanediyl group in which optionally one methylene
group is replaced by oxygen or sulfur and which is optionally mono-
to disubstituted by C.sub.1-C.sub.2-alkyl, C.sub.1-C.sub.2-alkoxy
or trifluoromethyl, [0159] or A and D together with the atoms to
which they are attached represent one of the groups AD-1 to
AD10
[0159] ##STR00021## [0160] G particularly preferably represents one
of the groups
[0160] ##STR00022## [0161] in which [0162] E represents a metal ion
equivalent or an ammonium ion, [0163] L represents oxygen or sulfur
and [0164] M represents oxygen or sulfur, [0165] R.sup.1
particularly preferably represents primary or secondary
C.sub.1-C.sub.10-alkyl, C.sub.2-C.sub.10-alkenyl,
C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.2-alkyl,
C.sub.1-C.sub.4-alkylthio-C.sub.1-C.sub.2-alkyl or
poly-C.sub.1-C.sub.3-alkoxy-C.sub.1-C.sub.2-alkyl, each of which is
optionally mono- to pentasubstituted by fluorine or chlorine,
monosubstituted by cyano or monosubstituted by CO--R.sup.13,
C.dbd.N--OR.sup.13 or CO.sub.2R.sup.13, or represents
C.sub.3-C.sub.6-cycloalkyl which is optionally mono- to
disubstituted by fluorine, chlorine, C.sub.1-C.sub.2-alkyl or
C.sub.1-C.sub.2-alkoxy and in which optionally one or two not
directly adjacent methylene groups are replaced by oxygen, [0166]
represents phenyl or benzyl, each of which is optionally mono- to
disubstituted by fluorine, chlorine, bromine, cyano, nitro,
C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkylthio,
C.sub.1-C.sub.4-alkylsulfinyl, C.sub.1-C.sub.4-alkylsulfonyl,
C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.2-haloalkyl or
C.sub.1-C.sub.2-haloalkoxy, [0167] represents pyrazolyl, thiazolyl,
pyridyl, pyrimidyl, furanyl or thienyl, each of which is optionally
mono- to disubstituted by fluorine, chlorine, bromine or
C.sub.1-C.sub.2-alkyl, [0168] R.sup.2 particularly preferably
represents C.sub.1-C.sub.10-alkyl, C.sub.2-C.sub.10-alkenyl,
C.sub.1-C.sub.4-alkoxy-C.sub.2-C.sub.4-alkyl or
poly-C.sub.1-C.sub.4-alkoxy-C.sub.2-C.sub.4-alkyl, each of which is
optionally mono- to trisubstituted by fluorine or chlorine, [0169]
represents C.sub.3-C.sub.7-cycloalkyl which is optionally
monosubstituted by C.sub.1-C.sub.2-alkyl or C.sub.1-C.sub.2-alkoxy
or [0170] represents phenyl or benzyl, each of which is optionally
mono- to disubstituted by fluorine, chlorine, bromine, cyano,
nitro, C.sub.1-C.sub.4-alkyl, methoxy, trifluoromethyl or
trifluoromethoxy, [0171] R.sup.3 particularly preferably represents
C.sub.1-C.sub.4-alkyl which is optionally mono- to trisubstituted
by fluorine or chlorine or represents phenyl or benzyl, each of
which is optionally monosubstituted by fluorine, chlorine, bromine,
C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy, trifluoromethyl,
trifluoromethoxy, cyano or nitro, [0172] R.sup.4 and R.sup.5
independently of one another particularly preferably represent
C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.6-alkylamino, di(C.sub.1-C.sub.6-alkyl)amino,
C.sub.1-C.sub.6-alkylthio or C.sub.3-C.sub.4-alkenylthio, each of
which is optionally mono- to trisubstituted by fluorine or
chlorine, or represent phenyl, phenoxy or phenylthio, each of which
is optionally mono- to disubstituted by fluorine, chlorine,
bromine, nitro, cyano, C.sub.1-C.sub.3-alkoxy, trifluoromethoxy,
C.sub.1-C.sub.3-alkylthio, C.sub.1-C.sub.3-alkyl or
trifluoromethyl, [0173] R.sup.6 and R.sup.7 independently of one
another particularly preferably represent hydrogen, represent
C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-cycloalkyl,
C.sub.1-C.sub.4-alkoxy, C.sub.3-C.sub.6-alkenyl or
C.sub.1-C.sub.6-alkoxy-C.sub.2-C.sub.6-alkyl, each of which is
optionally mono- to trisubstituted by fluorine or chlorine,
represent phenyl which is optionally mono- to disubstituted by
fluorine, chlorine, bromine, trifluoromethyl, C.sub.1-C.sub.4-alkyl
or C.sub.1-C.sub.4-alkoxy, or together represent a
C.sub.5-C.sub.6-alkylene radical which is optionally mono- to
disubstituted by methyl in which optionally one methylene group is
replaced by oxygen, [0174] R.sup.13 particularly preferably
represents C.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.4-alkenyl,
C.sub.3-C.sub.4-alkynyl, or
C.sub.1-C.sub.4-alkoxy-C.sub.2-C.sub.3-alkyl or represents
C.sub.3-C.sub.6-cycloalkyl in each optionally one methylene group
is replaced by oxygen.
[0175] In the radical definitions mentioned as being preferred,
halogen represents fluorine, chlorine, bromine and iodine, in
particular fluorine, chlorine and bromine. [0176] A very
particularly preferably represents hydrogen, methyl, ethyl,
n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl,
trifluoromethyl, methoxymethyl, ethoxymethyl, cyclopropyl,
cyclopentyl or cyclohexyl, [0177] B very particularly preferably
represents hydrogen, methyl or ethyl, or [0178] A, B and the carbon
atom to which they are attached very particularly preferably
represent saturated C.sub.6-cycloalkyl in which optionally one
methylene group is replaced by oxygen and which is optionally
substituted by methyl, ethyl, trifluoromethyl, methoxy, ethoxy,
n-propoxy, n-butyoxy or isobutoxy, and [0179] D very particularly
preferably represents hydrogen, or [0180] A very particularly
preferably represents hydrogen, methyl or ethyl, [0181] B very
particularly preferably represents hydrogen, and [0182] D very
particularly preferably represents methyl, ethyl, n-propyl,
isopropyl, n-butyl, sec-butyl, isobutyl, cyclopropyl, cyclopentyl
or cyclohexyl, or [0183] A and D together very particularly
preferably represent a C.sub.3-C.sub.4-alkanediyl group in which in
each case optionally one methylene group is replaced by oxygen or
sulfur and which is optionally mono- to disubstituted by methyl or
methoxy, or [0184] A and D together with the atoms to which they
are attached very particularly preferably represent the groups
below:
[0184] ##STR00023## [0185] G very particularly preferably
represents one of the groups
[0185] ##STR00024## [0186] L represents oxygen and [0187] M
represents oxygen or sulfur, [0188] R.sup.1 very particularly
preferably represents primary or secondary C.sub.1-C.sub.6-alkyl,
C.sub.2-C.sub.6-alkenyl,
C.sub.1-C.sub.2-alkoxy-C.sub.1-C.sub.2-alkyl,
C.sub.1-C.sub.2-alkylthio-C.sub.1-C.sub.2-alkyl or
poly-C.sub.1-C.sub.2-alkoxy-C.sub.1-C.sub.2-alkyl, each of which is
optionally mono- to trisubstituted by fluorine or chlorine, or
represents cyclopropyl, cyclopentyl or cyclohexyl, each of which is
optionally monosubstituted by fluorine, chlorine, methyl, ethyl or
methoxy, [0189] represents phenyl which is optionally
monosubstituted by fluorine, chlorine, bromine, cyano, nitro,
methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, methylthio,
ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl,
ethylsulfonyl, trifluoromethyl or trifluoro-methoxy, [0190]
represents furanyl, thienyl or pyridyl, each of which is optionally
monosubstituted by chlorine, bromine or methyl, [0191] R.sup.2 very
particularly preferably represents C.sub.1-C.sub.8-alkyl,
C.sub.2-C.sub.6-alkenyl or
C.sub.1-C.sub.3-alkoxy-C.sub.2-C.sub.3-alkyl, cyclopentyl or
cyclohexyl, [0192] or represents phenyl or benzyl, each of which is
optionally monosubstituted by fluorine, chlorine, bromine, cyano,
nitro, methyl, methoxy, trifluoromethyl or trifluoromethoxy, [0193]
R.sup.4 very particularly preferably represents
C.sub.1-C.sub.6-alkoxy, [0194] R.sup.5 very particularly preferably
represents C.sub.1-C.sub.6-alkoxy, [0195] R.sup.6 very particularly
preferably represents hydrogen, represents C.sub.1-C.sub.4-alkyl,
C.sub.3-C.sub.6-cycloalkyl or allyl, represents phenyl which is in
each case optionally monosubstituted by fluorine, chlorine,
bromine, methyl, methoxy or trifluoromethyl, [0196] R.sup.7 very
particularly preferably represents methyl, ethyl, n-propyl,
isopropyl or allyl, [0197] R.sup.6 and R.sup.7 together very
particularly preferably represent a C.sub.5-C.sub.6-alkylene
radical in which optionally one methylene group is replaced by
oxygen. [0198] A especially preferably represents methyl, ethyl or
cyclopropyl, [0199] B especially preferably represents methyl or
ethyl, [0200] A, B and the carbon atom to which they are attached
especially preferably represent saturated C.sub.6-cycloalkyl which
is optionally substituted by methyl or methoxy, [0201] D especially
preferably represents hydrogen, or [0202] A especially preferably
represents methyl or ethyl, [0203] B especially preferably
represents hydrogen, [0204] D especially preferably represents
methyl, ethyl or cyclopropyl, [0205] A and D together especially
preferably represent a C.sub.3-C.sub.4-alkanediyl group which is
optionally monosubstituted by methoxy, [0206] A and D together with
the atoms to which they are attached especially preferably
represent the groups AD-1 and AD-2, [0207] G especially preferably
represents one of the groups
[0207] ##STR00025## [0208] R.sup.1 especially preferably represents
primary or secondary C.sub.1-C.sub.6-alkyl,
C.sub.2-C.sub.6-alkenyl,
C.sub.1-C.sub.2-alkoxy-C.sub.1-C.sub.2-alkyl,
C.sub.1-C.sub.2-alkylthio-C.sub.1-C.sub.2-alkyl or
poly-C.sub.1-C.sub.2-alkoxy-C.sub.1-C.sub.2-alkyl, each of which is
optionally mono- to trisubstituted by fluorine or chlorine, or
represents cyclopropyl, cyclopentyl or cyclohexyl, each of which is
optionally monosubstituted by fluorine, chlorine, methyl, ethyl or
methoxy, [0209] represents phenyl which is optionally
monosubstituted by fluorine, chlorine, bromine, cyano, nitro,
methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, methylthio,
ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl,
ethylsulfonyl, trifluoromethyl or trifluoromethoxy, [0210]
represents furanyl, thienyl or pyridyl, each of which is optionally
monosubstituted by chlorine, bromine or methyl, (and represents in
particular primary or secondary C.sub.1-C.sub.6-alkyl or
C.sub.1-C.sub.2-alkoxy-C.sub.1-C.sub.2-alkyl), [0211] R.sup.2
especially preferably represents C.sub.1-C.sub.8-alkyl,
C.sub.2-C.sub.6-alkenyl or
C.sub.1-C.sub.3-alkoxy-C.sub.2-C.sub.3-alkyl, cyclopentyl or
cyclohexyl, [0212] or represents phenyl or benzyl, each of which is
optionally monosubstituted by fluorine, chlorine, bromine, cyano,
nitro, methyl, methoxy, trifluoromethyl or trifluoromethoxy, (and
represents in particular C.sub.1-C.sub.8-alkyl or
C.sub.2-C.sub.6-alkenyl), [0213] R.sup.4 especially preferably
represents C.sub.1-C.sub.6-alkoxy, [0214] R.sup.5 especially
preferably represents C.sub.1-C.sub.6-alkoxy.
[0215] The general or preferred radical definitions or
illustrations given above can be combined with one another as
desired, i.e. including combinations between the respective ranges
and preferred ranges. They apply both to the end products and,
correspondingly, to precursors and intermediates.
[0216] Preference according to the invention is given to the
compounds of the formula (I) which contain a combination of the
meanings given above as being preferred (preferably).
[0217] Particular preference according to the invention is given to
the compounds of the formula (I) which contain a combination of the
meanings given above as being particularly preferred.
[0218] Very particular preference according to the invention is
given to the compounds of the formula (I) which contain a
combination of the meanings given above as being very particularly
preferred.
[0219] Special preference according to the invention is given to
the compounds of the formula (I) which contain a combination of the
meanings given above as being especially preferred.
[0220] Saturated or unsaturated hydrocarbon radicals, such as
alkyl, alkanediyl or alkenyl, can in each case be straight-chain or
branched as far as this is possible, including in the combination
with heteroatoms, such as, for example, in alkoxy.
[0221] Unless indicated otherwise, optionally substituted radicals
can be mono- or polysubstituted, where in the case of
polysubstitution the substituents can be identical or
different.
[0222] In addition to the compounds mentioned in the preparation
examples, particular mention may be made of the following compounds
of the formulae (I-b) and (I-c):
TABLE-US-00001 TABLE 1 ##STR00026## A B --(CH.sub.2).sub.2--
--(CH.sub.2).sub.4-- --(CH.sub.2).sub.5-- --(CH.sub.2).sub.6--
--(CH.sub.2).sub.7-- --(CH.sub.2).sub.2--O--(CH.sub.2).sub.2--
--CH.sub.2--O--(CH.sub.2).sub.3--
--(CH.sub.2).sub.2--S--(CH.sub.2).sub.2--
--CH.sub.2--CHCH.sub.3--(CH.sub.2).sub.3--
--(CH.sub.2).sub.2--CHCH.sub.3--(CH.sub.2).sub.2--
--(CH.sub.2).sub.2--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--CHO--C.sub.4H.sub.9--(CH.sub.2).sub.2--
--(CH.sub.2).sub.2--CH--O-i-C.sub.4H.sub.9--(CH.sub.2).sub.2--
--(CH.sub.2).sub.2--C(CH.sub.3).sub.2--(CH.sub.2).sub.2--
--CH.sub.2--(CHCH.sub.3).sub.2--(CH.sub.2).sub.2--
A and B as defined in table 1,
TABLE-US-00002 Table 2 G = CH.sub.3--CO Table 3 G =
C.sub.2H.sub.5--CO Table 4 G = C.sub.3H.sub.7--CO Table 5 G =
i-C.sub.3H.sub.7--CO Table 6 G = C.sub.4H.sub.9--CO Table 7 G =
i-C.sub.4H.sub.9--CO Table 8 G = s-C.sub.4H.sub.9--CO Table 9 G =
t-C.sub.4H.sub.9--CO Table 10 ##STR00027## Table 11 G =
H.sub.3C--O--CH.sub.2--CO Table 12 G =
H.sub.5C.sub.2--O--CH.sub.2--CO Table 13 G =
H.sub.3C--S--CH.sub.2--CO Table 14 G =
H.sub.5C.sub.2--S--CH.sub.2--CO Table 15 G = CH.sub.3--O--CO Table
16 G = C.sub.2H.sub.5--O--CO Table 17 G = C.sub.3H.sub.7--O--CO
Table 18 G = i-C.sub.3H.sub.7--O--CO Table 19 G =
C.sub.4H.sub.9--O--CO Table 20 G = i-C.sub.4H.sub.9--O--CO Table 21
G = s-C.sub.4H.sub.9--O--CO Table 22 G = t-C.sub.4H.sub.9--O--CO
Table 23 G = t-C.sub.4H.sub.9--CH.sub.2--O--CO Table 24 G =
C.sub.6H.sub.5--CH.sub.2--O--CO Table 25 G = C.sub.6H.sub.5--O--CO
Table 26 G = CH.sub.3--S--CO Table 27 G = C.sub.2H.sub.5--S--CO
Table 28 G = C.sub.3H.sub.7--S--CO Table 29 G =
i-C.sub.3H.sub.7--S--CO Table 30 G = C.sub.4H.sub.9--S--CO Table 31
G = i-C.sub.4H.sub.9--S--CO Table 32 G = s-C.sub.4H.sub.9--S--CO
Table 33 G = t-C.sub.4H.sub.9--S--CO Table 34 G =
t-C.sub.4H.sub.9--CH.sub.2--S--CO Table 35 G =
C.sub.6H.sub.5--CH.sub.2--S--CO
[0223] Preferred meanings of the cyclic ketoenols, mentioned above
as active compounds in combination with the crop plant tolerance
promoter compounds (herbicide safeners), of the formula (I-a) are
defined below. [0224] G preferably represents hydrogen, [0225] A
preferably represents hydrogen, C.sub.2-C.sub.8-alkyl,
C.sub.1-C.sub.4-haloalkyl, represents C.sub.2-C.sub.8-alkenyl,
C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.4-alkyl or
C.sub.1-C.sub.6-alkylthio-C.sub.1-C.sub.4-alkyl, each of which is
optionally mono- to trisubstituted by halogen, represents
C.sub.3-C.sub.8-cycloalkyl which is optionally mono- to
trisubstituted by halogen, C.sub.1-C.sub.6-alkyl or
C.sub.1-C.sub.6-alkoxy, [0226] B preferably represents hydrogen,
C.sub.1-C.sub.6-alkyl or
C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.2-alkyl, or [0227] A, B and
the carbon atom to which they are attached preferably represent
C.sub.1-C.sub.6-alkyl-, C.sub.1-C.sub.6-alkoxy- or
C.sub.1-C.sub.4-haloalkyl-substituted saturated
C.sub.3-C.sub.8-cycloalkyl or represent unsaturated
C.sub.5-C.sub.8-cycloalkyl or represent C.sub.5-C.sub.8-cycloalkyl
in which one methylene group is replaced by oxygen or sulfur and
which is optionally mono- to disubstituted by
C.sub.1-C.sub.6-alkyl, [0228] D preferably represents hydrogen, or
[0229] A preferably represents hydrogen or C.sub.1-C.sub.8-alkyl,
[0230] B preferably represents hydrogen, [0231] D preferably
represents C.sub.2-C.sub.8-alkyl, C.sub.1-C.sub.8-alkenyl,
C.sub.1-C.sub.6-alkoxy-C.sub.2-C.sub.4-alkyl or
C.sub.1-C.sub.6-alkylthio-C.sub.2-C.sub.4-alkyl, each of which is
optionally mono- to pentasubstituted by halogen, represents
C.sub.3-C.sub.8-cycloalkyl which is optionally mono- to
trisubstituted by halogen, C.sub.1-C.sub.4-alkyl,
C.sub.1-C.sub.4-alkoxy or C.sub.1-C.sub.2-haloalkyl. [0232] A and D
together preferably represent a C.sub.3-C.sub.6-alkanediyl group or
C.sub.3-C.sub.6-alkenediyl group in which in each case optionally
one methylene group is replaced by oxygen or sulfur and which are
in each case optionally mono- to disubstituted by
C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy or
C.sub.1-C.sub.4-haloalkyl or by a further
C.sub.3-C.sub.6-alkanediyl, C.sub.3-C.sub.6-alkenediyl or
C.sub.4-C.sub.6-alkanedienediyl group which forms a fused-on ring,
[0233] G particularly preferably represents hydrogen, [0234] A
particularly preferably represents hydrogen, C.sub.2-C.sub.6-alkyl,
C.sub.1-C.sub.4-haloalkyl, represents C.sub.2-C.sub.6-alkenyl,
C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.3-alkyl or
C.sub.1-C.sub.4-alkylthio-C.sub.1-C.sub.3-alkyl, each of which is
optionally mono- to trisubstituted by fluorine or chlorine, or
represents C.sub.3-C.sub.6-cycloalkyl which is optionally mono- to
disubstituted by fluorine, chlorine, C.sub.1-C.sub.2-alkyl or
C.sub.1-C.sub.2-alkoxy, [0235] B particularly preferably represents
hydrogen, C.sub.1-C.sub.4-alkyl or
C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.2-alkyl, or [0236] A, B and
the carbon atom to which they are attached particularly preferably
represent saturated C.sub.3-C.sub.7-cycloalkyl which is substituted
by C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy or
C.sub.1-C.sub.2-haloalkyl or represent unsaturated
C.sub.5-C.sub.6-cycloalkyl or represent C.sub.5-C.sub.8-cycloalkyl
in which one methylene group is replaced by oxygen or sulfur and
which is optionally mono- to disubstituted by
C.sub.1-C.sub.4-alkyl, [0237] D particularly preferably represents
hydrogen, or [0238] A particularly preferably represents hydrogen
or C.sub.1-C.sub.6-alkyl, [0239] B particularly preferably
represents hydrogen, [0240] D particularly preferably represents
C.sub.2-C.sub.6-alkyl, C.sub.3-C.sub.6-alkenyl,
C.sub.1-C.sub.4-alkoxy-C.sub.2-C.sub.3-alkyl or
C.sub.1-C.sub.4-alkylthio-C.sub.2-C.sub.3-alkyl, each of which is
optionally mono- to trisubstituted by fluorine or chlorine,
represents C.sub.3-C.sub.6-cycloalkyl which is optionally mono- to
disubstituted by fluorine, chlorine, C.sub.1-C.sub.2-alkyl,
C.sub.1-C.sub.2-alkoxy or trifluoromethyl, [0241] A and D together
particularly preferably represent a C.sub.3-C.sub.5-alkanediyl
group in which optionally one methylene group is replaced by oxygen
or sulfur and which is optionally mono- to disubstituted by
C.sub.1-C.sub.2-alkyl, C.sub.1-C.sub.2-alkoxy or trifluoromethyl,
or A and D together with the atoms to which they are attached
represent one of the groups AD-1 to AD-10
[0241] ##STR00028## [0242] G very particularly preferably
represents hydrogen, [0243] A very particularly preferably
represents hydrogen, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,
sec-butyl, tert-butyl, trifluoromethyl, methoxymethyl,
ethoxymethyl, cyclopropyl, cyclopentyl or cyclohexyl, [0244] B very
particularly preferably represents hydrogen, methyl or ethyl, or
[0245] A, B and the carbon atom to which they are attached very
particularly preferably represent saturated C.sub.6-cycloalkyl
which is substituted by methyl, ethyl, trifluoromethyl, methoxy,
ethoxy, n-propoxy, n-butoxy or isobutoxy or represent
C.sub.6-cycloalkyl in which one methylene group is replaced by
oxygen and which is optionally monosubstituted by methyl or ethyl,
[0246] D very particularly preferably represents hydrogen or [0247]
A very particularly preferably represents hydrogen, methyl or
ethyl, [0248] B very particularly preferably represents hydrogen,
[0249] D very particularly preferably represents ethyl, n-propyl,
isopropyl, n-butyl, sec-butyl, isobutyl, cyclopropyl, cyclopentyl
or cyclohexyl, [0250] A and D together very particularly preferably
represent a C.sub.3-C.sub.4-alkanediyl group in which in each case
optionally one methylene group is replaced by oxygen or sulfur and
which is optionally mono- to disubstituted by methyl or [0251] A
and D together with the atoms to which they are attached represent
the group below:
##STR00029##
[0252] Special preference is given to the compounds of the formula
(I-a) listed in the table below:
TABLE-US-00003 (I-a) ##STR00030## A B D
--(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--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--CHO--C.sub.4H.sub.9--(CH.sub.2).sub.2-- H
--(CH.sub.2).sub.2--CH--O-i-C.sub.4H.sub.9--(CH.sub.2).sub.2 H
--(CH.sub.2).sub.2--C(CH.sub.3).sub.2--(CH.sub.2).sub.2-- H
--CH.sub.2--(CHCH.sub.3).sub.2--(CH.sub.2).sub.2-- H 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
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 ##STR00031## CH.sub.3 H ##STR00032##
CH.sub.3 H ##STR00033## CH.sub.3 H A D B 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 CH.sub.3 C.sub.2H.sub.5 H C.sub.2H.sub.5
C.sub.2H.sub.5 H H ##STR00034## H H ##STR00035## H H ##STR00036## H
--(CH.sub.2).sub.3-- H --(CH.sub.2).sub.4-- H
--CH.sub.2--S--(CH.sub.2).sub.2-- H ##STR00037## H
[0253] Preferred meanings of the groups listed above in connection
with the crop plant tolerance promoter compounds ("herbicide
safeners") of the formulae (IIa), (IIb), (IIc), (IId) and (IIe) are
defined below. [0254] m preferably represents the numbers 0, 1, 2,
3 or 4. [0255] A.sup.1 preferably represents one of the divalent
heterocyclic groupings shown below
[0255] ##STR00038## [0256] n preferably represents the numbers 0,
1, 2, 3 or 4. [0257] A.sup.2 preferably represents in each case
optionally methyl-, ethyl-, methoxycarbonyl- or ethoxycarbonyl- or
allyloxycarbonyl-substituted methylene or ethylene. [0258] R.sup.14
preferably represents hydroxyl, mercapto, amino, methoxy, ethoxy,
n- or i-propoxy, n-, i-, s- or t-butoxy, methylthio, ethylthio, n-
or i-propylthio, n-, i-, s- or t-butylthio, methylamino,
ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino,
dimethylamino or diethylamino. [0259] R.sup.15 preferably
represents hydroxyl, mercapto, amino, methoxy, ethoxy, n- or
i-propoxy, n-, i-, s- or t-butoxy, 1-methylhexyloxy, allyloxy,
1-allyloxymethylethoxy, methylthio, ethylthio, n- or i-propylthio,
n-, i-, s- or t-butylthio, methylamino, ethylamino, n- or
i-propylamino, n-, i-, s- or t-butylamino, dimethylamino or
diethylamino. [0260] R.sup.16 preferably represents in each case
optionally fluorine-, chlorine-, and/or bromine-substituted methyl,
ethyl, n- or i-propyl. [0261] R.sup.17 preferably represents
hydrogen, in each case optionally fluorine- and/or
chlorine-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or
t-butyl, propenyl, butenyl, propynyl or butynyl, methoxymethyl,
ethoxymethyl, methoxyethyl, ethoxyethyl, dioxolanylmethyl, furyl,
furyl-methyl, thienyl, thiazolyl, piperidinyl, or optionally
fluorine-, chlorine-, methyl-, ethyl-, n- or i-propyl-, n-, i-, s-
or t-butyl-substituted phenyl. [0262] R.sup.18 preferably
represents hydrogen, in each case optionally fluorine- and/or
chlorine-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or
t-butyl, propenyl, butenyl, propynyl or butynyl, methoxymethyl,
ethoxymethyl, methoxyethyl, ethoxyethyl, dioxolanylmethyl, furyl,
furyl-methyl, thienyl, thiazolyl, piperidinyl, or optionally
fluorine-, chlorine-, methyl-, ethyl-, n- or i-propyl-, n-, i-, s-
or t-butyl-substituted phenyl, or together with R.sup.17 represents
one of the radicals --CH.sub.2--O--CH.sub.2--CH.sub.2-- and
--CH.sub.2--CH.sub.2--O--CH.sub.2--CH.sub.2-- which are optionally
substituted by methyl, ethyl, furyl, phenyl, a fused benzene ring
or by two substituents which, together with the C atom to which
they are attached, form a 5- or 6-membered carbocycle. [0263]
R.sup.19 preferably represents hydrogen, cyano, fluorine, chlorine,
bromine, or represents in each case optionally fluorine-, chlorine-
and/or bromine-substituted methyl, ethyl, n- or i-propyl,
cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or phenyl. [0264]
R.sup.20 preferably represents hydrogen, optionally hydroxyl-,
cyano-, fluorine-, chlorine-, methoxy-, ethoxy-, n- or
i-propoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or
t-butyl. [0265] R.sup.21 preferably represents hydrogen, cyano,
fluorine, chlorine, bromine, or represents in each case optionally
fluorine-, chlorine- and/or bromine-substituted methyl, ethyl, n-
or i-propyl, n-, i-, s- or t-butyl, cyclopropyl, cyclobutyl,
cyclopentyl, cyclohexyl or phenyl. [0266] X.sup.1 preferably
represents nitro, cyano, fluorine, chlorine, bromine, methyl,
ethyl, n- or i-propyl, n-, i-, s- or t-butyl, difluoromethyl,
dichloromethyl, trifluoromethyl, trichloromethyl,
chlorodifluoromethyl, fluorodichloromethyl, methoxy, ethoxy, n- or
i-propoxy, difluoromethoxy or trifluoromethoxy. [0267] X.sup.2
preferably represents hydrogen, nitro, cyano, fluorine, chlorine,
bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl,
difluoromethyl, dichloromethyl, trifluoromethyl, trichloromethyl,
chlorodifluoromethyl, fluorodichloromethyl, methoxy, ethoxy, n- or
i-propoxy, difluoromethoxy or trifluoromethoxy. [0268] X.sup.3
preferably represents hydrogen, nitro, cyano, fluorine, chlorine,
bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl,
difluoromethyl, dichloromethyl, trifluoromethyl, trichloromethyl,
chlorodifluoromethyl, fluorodichloromethyl, methoxy, ethoxy, n- or
i-propoxy, difluoromethoxy or trifluoromethoxy. [0269] t preferably
represents the numbers 0, 1, 2, 3 or 4. [0270] v preferably
represents the numbers 0, 1, 2, or 3. [0271] R.sup.22 preferably
represents hydrogen, methyl, ethyl, n- or i-propyl. [0272] R.sup.23
preferably represents hydrogen, methyl, ethyl, n- or i-propyl.
[0273] R.sup.24 preferably represents hydrogen, in each case
optionally cyano-, fluorine-, chlorine-, methoxy-, ethoxy-, n- or
i-propoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or
t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy,
methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or
t-butylthio, methylamino, ethylamino, n- or i-propylamino, n-, i-,
s- or t-butylamino, dimethylamino or diethylamino, or in each case
optionally cyano-, fluorine-, chlorine-, bromine-, methyl-, ethyl-,
n- or i-propyl-substituted cyclopropyl, cyclobutyl, cyclopentyl,
cyclohexyl, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy,
cyclohexyloxy, cyclopropylthio, cyclobutylthio, cyclopentylthio,
cyclohexylthio, cyclopropylamino, cyclobutylamino, cyclopentylamino
or cyclohexylamino. [0274] R.sup.25 preferably represents hydrogen,
in each case optionally cyano-, hydroxyl-, fluorine-, chlorine-,
methoxy-, ethoxy-, n- or i-propoxy-substituted methyl, ethyl, n- or
i-propyl, n-, i- or s-butyl, in each case optionally cyano-,
fluorine-, chlorine- or bromine-substituted propenyl, butenyl,
propynyl or butynyl, or in each case optionally cyano-, fluorine-,
chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-substituted
cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. [0275] R.sup.26
preferably represents hydrogen, in each case optionally cyano-,
hydroxyl-, fluorine-, chlorine-, methoxy-, ethoxy-, n- or
i-propoxy-substituted methyl, ethyl, n- or i-propyl, n-, i- or
s-butyl, in each case optionally cyano-, fluorine-, chlorine- or
bromine-substituted propenyl, butenyl, propynyl or butynyl, in each
case optionally cyano-, fluorine-, chlorine-, bromine-, methyl-,
ethyl-, n- or i-propyl-substituted cyclopropyl, cyclobutyl,
cyclopentyl or cyclohexyl, or optionally nitro-, cyano-, fluorine-,
chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-, n-, i-, s-
or t-butyl-, trifluoromethyl-, methoxy-, ethoxy-, n- or i-propoxy-,
difluoromethoxy- or trifluoromethoxy-substituted phenyl, or
together with R.sup.25 represents in each case optionally methyl-
or ethyl-substituted butane-1,4-diyl (trimethylene),
pentane-1,5-diyl, 1-oxabutane-1,4-diyl or 3-oxapentane-1,5-diyl.
[0276] X.sup.4 preferably represents nitro, cyano, carboxyl,
carbamoyl, formyl, sulfamoyl, hydroxyl, amino, fluorine, chlorine,
bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl,
trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy
or trifluoromethoxy. [0277] X.sup.5 preferably represents nitro,
cyano, carboxyl, carbamoyl, formyl, sulfamoyl, hydroxyl, amino,
fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-,
s- or t-butyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy,
difluoromethoxy or trifluoromethoxy.
[0278] Examples of the compounds of the formula (IIa) which are
very particularly preferred as herbicide safeners according to the
invention are listed in the table below.
[0279] Table: Examples of the compounds of the formula (IIa)
TABLE-US-00004 (IIa) ##STR00039## Example (Positions) No.
(X.sup.1).sub.m A.sup.1 R.sup.14 IIa-1 (2) Cl, (4) Cl ##STR00040##
OCH.sub.3 IIa-2 (2) Cl, (4) Cl ##STR00041## OCH.sub.3 IIa-3 (2) Cl,
(4) Cl ##STR00042## OC.sub.2H.sub.5 IIa-4 (2) Cl, (4) Cl
##STR00043## OC.sub.2H.sub.5 IIa-5 (2) Cl ##STR00044## OCH.sub.3
IIa-6 (2) Cl, (4) Cl ##STR00045## OCH.sub.3 IIa-7 (2) F
##STR00046## OCH.sub.3 IIa-8 (2) F ##STR00047## OCH.sub.3 IIa-9 (2)
Cl, (4) Cl ##STR00048## OC.sub.2H.sub.5 IIa-10 (2) Cl, (4) CF.sub.3
##STR00049## OCH.sub.3 IIa-11 (2) Cl ##STR00050## OCH.sub.3 IIa-12
-- ##STR00051## OC.sub.2H.sub.5 IIa-13 (2) Cl, (4) Cl ##STR00052##
OC.sub.2H.sub.5 IIa-14 (2) Cl, (4) Cl ##STR00053## OC.sub.2H.sub.5
IIa-15 (2) Cl, (4) Cl ##STR00054## OC.sub.2H.sub.5 IIa-16 (2) Cl,
(4) Cl ##STR00055## OC.sub.2H.sub.5 IIa-17 (2) Cl, (4) Cl
##STR00056## OC.sub.2H.sub.5 IIa-18 -- ##STR00057## OH
[0280] Examples of the compounds of the formula (IIb) which are
very particularly preferred as herbicide safeners according to the
invention are listed in the table below.
TABLE-US-00005 TABLE (IIb) ##STR00058## Examples of the compounds
of the formula (IIb) Ex- am- ple (Position) (Position) No. X.sup.2
X.sup.3 A.sup.2 R.sup.15 IIb-1 (5) Cl -- CH.sub.2 OH IIb-2 (5) Cl
-- CH.sub.2 OCH.sub.3 IIb-3 (5) Cl -- CH.sub.2 OC.sub.2H.sub.5
IIb-4 (5) Cl -- CH.sub.2 OC.sub.3H.sub.7-n IIb-5 (5) Cl -- CH.sub.2
OC.sub.3H.sub.7-i IIb-6 (5) Cl -- CH.sub.2 OC.sub.4H.sub.9-n IIb-7
(5) Cl -- CH.sub.2 OCH(CH.sub.3)C.sub.5H.sub.11-n IIb-8 (5) Cl (2)
F CH.sub.2 OH IIb-9 (5) Cl (2) Cl CH.sub.2 OH IIb-10 (5) Cl --
CH.sub.2 OCH.sub.2CH.dbd.CH.sub.2 IIb-11 (5) Cl -- CH.sub.2
OC.sub.4H.sub.9-i IIb-12 (5) Cl -- CH.sub.2 ##STR00059## IIb-13 (5)
Cl -- ##STR00060## OCH.sub.2CH.dbd.CH.sub.2 IIb-14 (5) Cl --
##STR00061## OC.sub.2H.sub.5 IIb-15 (5) Cl -- ##STR00062##
OCH.sub.3
[0281] Examples of the compounds of the formula (IIc) which are
very particularly preferred as herbicide safeners according to the
invention are listed in the table below.
##STR00063##
[0282] Table: Examples of the compounds of the formula (IIc)
TABLE-US-00006 Example No. R.sup.16 N(R.sup.17,R.sup.18) IIc-1
CHCl.sub.2 N(CH.sub.2CH.dbd.CH.sub.2).sub.2 IIc-2 CHCl.sub.2
##STR00064## IIc-3 CHCl.sub.2 ##STR00065## IIc-4 CHCl.sub.2
##STR00066## IIc-5 CHCl.sub.2 ##STR00067## IIc-6 CHCl.sub.2
##STR00068## IIc-7 CHCl.sub.2 ##STR00069##
[0283] Examples of the compounds of the formula (IId) which are
very particularly preferred as herbicide safeners according to the
invention are listed in the table below.
TABLE-US-00007 TABLE (IId) ##STR00070## Examples of the compounds
of the formula (IId) Example (Positions) (Positions) No. R.sup.22
R.sup.23 R.sup.24 (X.sup.4).sub.t (X.sup.5).sub.v IId-1 H H
CH.sub.3 (2) OCH.sub.3 -- IId-2 H H C.sub.2H.sub.5 (2) OCH.sub.3 --
IId-3 H H C.sub.3H.sub.7-n (2) OCH.sub.3 -- IId-4 H H
C.sub.3H.sub.7-i (2) OCH.sub.3 -- IId-5 H H ##STR00071## (2)
OCH.sub.3 -- IId-6 H H CH.sub.3 (2) OCH.sub.3 -- (5) CH.sub.3 IId-7
H H C.sub.2H.sub.5 (2) OCH.sub.3 -- (5) CH.sub.3 IId-8 H H
C.sub.3H.sub.7-n (2) OCH.sub.3 -- (5) CH.sub.3 IId-9 H H
C.sub.3H.sub.7-i (2) OCH.sub.3 -- (5) CH.sub.3 IId-10 H H
##STR00072## (2) OCH.sub.3(5) CH.sub.3 -- IId-11 H H OCH.sub.3 (2)
OCH.sub.3 -- (5) CH.sub.3 IId-12 H H OC.sub.2H.sub.5 (2) OCH.sub.3
-- (5) CH.sub.3 IId-13 H H OC.sub.3H.sub.7-i (2) OCH.sub.3 -- (5)
CH.sub.3 IId-14 H H SCH.sub.3 (2) OCH.sub.3 -- (5) CH.sub.3 IId-15
H H SC.sub.2H.sub.5 (2) OCH.sub.3 -- (5) CH.sub.3 IId-16 H H
SC.sub.3H.sub.7-i (2) OCH.sub.3 -- (5) CH.sub.3 IId-17 H H
NHCH.sub.3 (2) OCH.sub.3 -- (5) CH.sub.3 IId-18 H H
NHC.sub.2H.sub.5 (2) OCH.sub.3 -- (5) CH.sub.3 IId-19 H H
NHC.sub.3H.sub.7-i (2) OCH.sub.3 -- (5) CH.sub.3 IId-20 H H
##STR00073## (2) OCH.sub.3(5) CH.sub.3 -- IId-21 H H NHCH.sub.3 (2)
OCH.sub.3 -- IId-22 H H NHC.sub.3H.sub.7-i (2) OCH.sub.3 -- IId-23
H H N(CH.sub.3).sub.2 (2) OCH.sub.3 -- IId-24 H H N(CH.sub.3).sub.2
(3) CH.sub.3 -- (4) CH.sub.3 IId-25 H H CH.sub.2--O--CH.sub.3 (2)
OCH.sub.3 --
[0284] Examples of the compounds of the formula (IIe) which are
very particularly preferred as herbicide safeners according to the
invention are listed in the table below.
TABLE-US-00008 TABLE (IIe) ##STR00074## Examples of the compounds
of the formula (IIe) Example (Positions) (Positions) No. R.sup.22
R.sup.25 R.sup.26 (X.sup.4).sub.t (X.sup.5).sub.v IIe-1 H H
CH.sub.3 (2) OCH.sub.3 -- IIe-2 H H C.sub.2H.sub.5 (2) OCH.sub.3 --
IIe-3 H H C.sub.3H.sub.7-n (2) OCH.sub.3 -- IIe-4 H H
C.sub.3H.sub.7-i (2) OCH.sub.3 -- IIe-5 H H ##STR00075## (2)
OCH.sub.3 -- IIe-6 H CH.sub.3 CH.sub.3 (2) OCH.sub.3 -- IIe-7 H H
CH.sub.3 (2) OCH.sub.3 -- (5) CH.sub.3 IIe-8 H H C.sub.2H.sub.5 (2)
OCH.sub.3 -- (5) CH.sub.3 IIe-9 H H C.sub.3H.sub.7-n (2) OCH.sub.3
-- (5) CH.sub.3 IIe-10 H H C.sub.3H.sub.7-i (2) OCH.sub.3 -- (5)
CH.sub.3 IIe-11 H H ##STR00076## (2) OCH.sub.3(5) CH.sub.3 --
IIe-12 H CH.sub.3 CH.sub.3 (2) OCH.sub.3 -- (5) CH.sub.3
[0285] Most preferred as crop plant tolerance promoter compound
[component (c')] are cloquintocet-mexyl, fenchlorazole-ethyl,
isoxadifen-ethyl, mefenpyr-diethyl, furilazole, fenclorim,
cumyluron, dymron, dimepiperate and the compounds IIe-5 and IIe-11,
and particular emphasis is given to cloquintocet-mexyl and
mefenpyr-diethyl.
[0286] Examples of the selective-herbicidal combinations according
to the invention comprising in each case one active compound of the
formula (I) and one of the safeners defined above are listed in the
table below.
TABLE-US-00009 TABLE Examples of the combinations according to the
invention Active compounds of the formula (I) Safeners I-a
cloquintocet-mexyl I-a fenchlorazole-ethyl I-a isoxadifen-ethyl I-a
mefenpyr-diethyl I-a furilazole I-a fenclorim I-a cumyluron I-a
daimuron/dymron I-a dimepiperate I-a IIe-11 I-a IIe-5 I-b
cloquintocet-mexyl I-b fenchlorazole-ethyl I-b isoxadifen-ethyl I-b
mefenpyr-diethyl I-b furilazole I-b fenclorim I-b cumyluron I-b
daimuron/dymron I-b dimepiperate I-b IIe-11 I-b IIe-5 I-c
cloquintocet-mexyl I-c fenchlorazole-ethyl I-c isoxadifen-ethyl I-c
mefenpyr-diethyl I-c furilazole I-c fenclorim I-c cumyluron I-c
daimuron/dymron I-c dimepiperate I-c IIe-5 I-c IIe-11 I-d
cloquintocet-mexyl I-d fenchlorazole-ethyl I-d isoxadifen-ethyl I-d
mefenpyr-diethyl I-d furilazole I-d fenclorim I-d cumyluron I-d
daimuron/dymron I-d dimepiperate I-d IIe-11 I-d IIe-5 I-e
cloquintocet-mexyl I-e fenchlorazole-ethyl I-e isoxadifen-ethyl I-e
mefenpyr-diethyl I-e furilazole I-e fenclorim I-e cumyluron I-e
daimuron/dymron I-e dimepiperate I-e IIe-5 I-e IIe-11 I-f
cloquintocet-mexyl I-f fenchlorazole-ethyl I-f isoxadifen-ethyl I-f
mefenpyr-diethyl I-f furilazole I-f fenclorim I-f cumyluron I-f
daimuron/dymron I-f dimepiperate I-f IIe-5 I-f IIe-11 I-g
cloquintocet-mexyl I-g fenchlorazole-ethyl I-g isoxadifen-ethyl I-g
mefenpyr-diethyl I-g furilazole I-g fenclorim I-g cumyluron I-g
daimuron/dymron I-g dimepiperate I-g IIe-5 I-g IIe-11
[0287] The compounds of the general formula (IIa) to be used as
safeners according to the invention are known and/or can be
prepared by processes known per se (cf. WO-A-91/07874,
WO-A-95/07897).
[0288] The compounds of the general formula (IIb) to be used as
safeners according to the invention are known and/or can be
prepared by processes known per se (cf. EP-A-191736).
[0289] The compounds of the general formula (IIc) to be used as
safeners according to the invention are known and/or can be
prepared by processes known per se (cf. DE-A-2218097,
DE-A-2350547).
[0290] The compounds of the general formula (IId) to be used as
safeners according to the invention are known and/or can be
prepared by processes known per se (cf. DE-A-19621522/U.S. Pat. No.
6,235,680).
[0291] The compounds of the general formula (IIe) to be used as
safeners according to the invention are known and can be prepared
by processes known per se (cf. WO-A-99/66795/U.S. Pat. No.
6,251,827).
[0292] It has now surprisingly been found that the above-defined
active-compound combinations of substituted ketoenols of the
general formula (I) and (I-a) and safeners (antidotes) from the
component (c') set out above combine very good useful plant
tolerance with a high herbicidal activity and can be used in
various crops, in particular in cereals (especially wheat), but
also in soybeans, potatoes, maize and rice, for selective weed
control.
[0293] In this context it is considered surprising that, from a
multiplicity of known safeners or antidotes capable of antagonizing
the damaging effect of a herbicide on the crop plants, it is
specifically the compounds of component (c') set out above which
are suitable for compensating--almost completely--the damaging
effect of substituted cyclic ketoenols on the crop plants, without
at the same time having any critical adverse effect on the
herbicidal activity against the weeds.
[0294] Emphasis may be given here to the particularly advantageous
effect of the particularly preferred and most preferred combination
partners from component (c'), particularly with regard to the
gentle treatment of cereal plants, such as wheat, barley and rye,
for example, but also maize and rice, as crop plants.
[0295] Using, for example, according to process (B.alpha.)
8-methyl-3-(2,6-diethyl-4-methylphenyl)-1-azaspiro[4,5]decane-2,4-dione
and isobutyl chloride as starting materials, the course of the
process according to the invention can be represented by the
reaction scheme below:
##STR00077##
[0296] Using, for example, according to process (B) (variant
.beta.)
8-methoxy-3-(2,6-diethyl-4-methylphenyl)-1-azaspiro[4,5]decane-2,4-dione
and acetic anhydride as starting materials, the course of the
process according to the invention can be represented by the
reaction scheme below:
##STR00078##
[0297] Using, for example, according to process (C) 8-methoxy
3-(2,6-diethyl-4-methylphenyl)-1-azaspiro[4,5]decane-2,4-dione and
ethyl chloraformate as starting materials, the course of the
process according to the invention can be represented by the
reaction scheme below:
##STR00079##
[0298] Using, for example, according to process (D), variant a
8-methyl
3-(2,6-diethyl-4-methylphenyl)-1-azaspiro[4,5]decane-2,4-dione and
methyl chloromonothioformate as starting materials, the course of
the reaction can be represented as follows:
##STR00080##
[0299] Using, for example, according to process (D), variant .beta.
8-methoxy-3-(2,6-diethyl-4-methylphenyl)-1-azaspiro[4,5]decane-2,4-dione,
carbon disulfide and methyl iodide as starting components, the
course of the reaction can be represented as follows:
##STR00081##
[0300] Using, for example, according to process (E)
8-methyl-3-(2,6-diethyl-4-methylphenyl)-1-azaspiro[4,5]decane-2,4-dione
and methanesulfonyl chloride as starting material, the course of
the reaction can be represented by the reaction scheme below:
##STR00082##
[0301] Using, for example, according to process (F) 8-methoxy
3-(2,6-diethyl-4-methylphenyl)-1-azaspiro[4,5]decane-2,4-dione and
(2,2,2-trifluoroethyl)methanethiophosphonyl chloride as starting
materials, the course of the reaction can be represented by the
reaction scheme below:
##STR00083##
[0302] Using, for example, according to process (G)
8-methoxy-3-(2,6-diethyl-4-methylphenyl)-1-azaspiro[4,5]decane-2,4-dione
and NaOH as components, the course of the process according to the
invention can be represented by the reaction scheme below:
##STR00084##
[0303] Using, for example, according to process (H) variant a
8-methoxy
3-(2,6-diethyl-4-methylphenyl)-1-azaspiro[4,5]decane-2,4-dione and
ethyl isocyanate as starting materials, the course of the reaction
can be represented by the reaction scheme below:
##STR00085##
[0304] Using, for example, according to process (H) variant .beta.
8-methoxy-3-(2,6-diethyl-4-methylphenyl)-1-azaspiro[4,5]decane-2,4-dione
and dimethylcarbamoyl chloride as starting materials, the course of
the reaction can be represented by the scheme below:
##STR00086##
[0305] Some of the compounds, required as starting materials in the
process (A) according to the invention, of the formula (Ia)
##STR00087##
in which A, B and D are as defined above are novel (WO 01/17972, WO
01/74770) or they can be prepared by the processes described
therein in principle.
[0306] The acid halides of the formula (II), carboxylic anhydrides
of the formula (III), chloroformic esters or chloroformic
thioesters of the formula (IV), chloromonothioformic esters or
chlorodithioformic esters of the formula (V), alkyl halides of the
formula (VI), sulfonyl chlorides of the formula (VII), phosphorus
compounds of the formula (VIII) and metal hydroxides, metal
alkoxides or amines of the formula (IX) and (X) and isocyanates of
the formula (XI) and carbamoyl chlorides of the formula (XII)
furthermore required as starting materials for carrying out the
processes (A), (B), (C), (D), (E), (F) and (G) according to the
invention are generally known compounds of organic or inorganic
chemistry.
[0307] The process (A.alpha.) is characterized in that compounds of
the formula (I-a) are in each case reacted with carbonyl halides of
the formula (II), if appropriate in the presence of a diluent and
if appropriate in the presence of an acid binder.
[0308] Suitable diluents for use in the process (A.alpha.)
according to the invention are all solvents which are inert to the
acid halides. Preference is given to using hydrocarbons, such as
benzine, benzene, toluene, xylene and tetraline, furthermore
halogenated hydrocarbons, such as methylene chloride, chloroform,
carbon tetrachloride, chlorobenzene and o-dichlorobenzene, moreover
ketones, such as acetone and methyl isopropyl ketone, furthermore
ethers, such as diethyl ether, tetrahydrofuran and dioxane,
additionally carboxylic esters, such as ethyl acetate, and also
strongly polar solvents, such as dimethyl sulfoxide and sulfolane.
The hydrolytic stability of the acid halide permitting, the
reaction can also be carried out in the presence of water.
[0309] Suitable acid binders for the reaction according to process
(A.alpha.) according to the invention are all customary acid
acceptors. Preference is given to using tertiary amines, such as
triethylamine, pyridine, diazabicyclooctane (DABCO),
diazabicycloundecene (DBU), diazabicyclononene (DBN), Hunig base
and N,N-dimethylaniline, furthermore alkaline earth metal oxides,
such as magnesium oxide and calcium oxide, moreover alkali metal
and alkaline earth metal carbonates, such as sodium carbonate,
potassium carbonate and calcium carbonate, and also alkali metal
hydroxides, such as sodium hydroxide and potassium hydroxide.
[0310] The reaction temperature in the process (A.alpha.) according
to the invention may be varied within a relatively wide range. In
general, the process is carried out at temperatures between
-20.degree. C. and +150.degree. C., preferably between 0.degree. C.
and 100.degree. C.
[0311] When carrying out the process (A.alpha.) according to the
invention, the starting materials of the formula (I-a) and the
carbonyl halide of the formula (II) are generally each employed in
approximately equivalent amounts. However, it is also possible to
use a relatively large excess (up to 5 mol) of the carbonyl halide.
Work-up is carried out by customary methods.
[0312] The process (A.beta.) is characterized in that compounds of
the formula (I-a) are in each case reacted with carboxylic
anhydrides of the formula (III), if appropriate in the presence of
a diluent and if appropriate in the presence of an acid binder.
[0313] Suitable diluents for use in the process (A.beta.) according
to the invention are, preferably, those diluents which are also
preferred when acid halides are used. Besides, it is also possible
for excess carboxylic anhydride to act simultaneously as
diluent.
[0314] Suitable optional binders in the process (A.beta.) are,
preferably, those acid binders which are also preferred when acid
halides are used.
[0315] The reaction temperature in the process (A.beta.) according
to the invention can be varied within a relatively wide range. In
general, the process is carried out at temperatures between
-20.degree. C. and +150.degree. C., preferably between 0.degree. C.
and 100.degree. C.
[0316] When carrying out the process (A.beta.) according to the
invention, the starting materials of the formula (I-a) and the
carboxylic anhydride of the formula (III) 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.
[0317] In general, diluent and excess carboxylic anhydride and also
the carboxylic acid formed are removed by distillation or by
washing with an organic solvent or with water.
[0318] The process (B) is characterized in that compounds of the
formula (I-a) are in each case reacted with chloroformic esters or
chloroformic thioesters of the formula (IV), if appropriate in the
presence of a diluent and if appropriate in the presence of an acid
binder.
[0319] Suitable acid binders for the process (B) 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-dimethylaniline, furthermore, alkaline
earth metal oxides, such as magnesium oxide and calcium oxide,
moreover alkali metal and alkaline earth metal carbonates, such as
sodium carbonate, potassium carbonate and calcium carbonate, and
also alkali metal hydroxides, such as sodium hydroxide and
potassium hydroxide.
[0320] Suitable diluents for use in the process (B) according to
the invention are all solvents which are inert to the chloroformic
esters or chloroformic thioesters. Preference is given to using
hydrocarbons, such as benzine, benzenes, toluene, xylene and
tetraline, furthermore halogenated hydrocarbons, such as methylene
chloride, chloroform, carbon tetrachloride, chlorobenzene and
o-dichlorobenzene, moreover ketones, such as acetone and methyl
isopropyl ketone, furthermore ethers, such as diethyl ether,
tetrahydrofuran and dioxane, additional carboxylic esters, such as
ethyl acetate, and also strongly polar solvents, such as dimethyl
sulfoxide and sulfolane.
[0321] When carrying out the process (B) according to the
invention, the reaction temperature may be varied within a
relatively wide range. In general, the reaction temperature is
between -20.degree. C. and +100.degree. C., preferably between
0.degree. C. and 50.degree. C.
[0322] The process (B) according to the invention is generally
carried out under atmospheric pressure.
[0323] When carrying out the process (B) according to the
invention, the starting materials of the formula (I-a) and the
appropriate chloroformic ester or chloroformic thioester of the
formula (IV) are generally each employed in approximately
equivalent amounts. However, it is also possible to use a
relatively large excess (up to 20 mol) of one component or the
other. Work-up is carried out by customary methods. In general,
precipitated salts are removed and the reaction mixture that
remains is concentrated by removing the diluent under reduced
pressure.
[0324] The process (C) according to the invention is characterized
in that compounds of the formula (I-a) are in each case reacted
with (C.alpha.) compounds of the formula (V) in the presence of a
diluent and, if appropriate, in the presence of an acid binder or
(C.beta.) carbon disulfide and subsequently with alkyl halides of
the formula (VI), if appropriate in the presence of a diluent and
if appropriate in the presence of a base.
[0325] In preparation process (C.alpha.), about 1 mol of
chloromonothioformic ester or chlorodithioformic ester of the
formula (VI) is reacted per mole of the starting material of the
formula (I-a), at from 0 to 120.degree. C., preferably from 20 to
60.degree. C.
[0326] Suitable diluents which are added, if appropriate, are all
inert polar organic solvents, such as ethers, esters, amides,
sulfones, sulfoxides, and also halogenated alkanes.
[0327] Preference is given to using dimethyl sulfoxide, ethyl
acetate, tetrahydrofuran, dimethylformamide or methylene
chloride.
[0328] If, in a preferred embodiment, the enolate salt of the
compound (I-a) is prepared by adding strong deprotonating agents,
such as, for example, sodium hydride or potassium tert-butoxide,
the further addition of acid binders may be dispensed with.
[0329] If acid binders are used, these are customary inorganic or
organic bases, for example sodium hydroxide, sodium carbonate,
potassium carbonate, pyridine and triethylamine.
[0330] 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.
[0331] In preparation process (C.beta.), in each case an aquimolar
amount of in excess of carbon disulfide is added per mole of
starting materials of the formula (I-a). Here, the process is
preferably carried out at temperatures of from 0 to 50.degree. C.
and in particular at from 20 to 30.degree. C.
[0332] Frequently, it is expedient to prepare initially the
corresponding salt from the compounds of the formula (I-a) by
adding a base (such as, for example, potassium tert-butoxide or
sodium hydride). In each case, the compound (I-a) is reacted with
carbon disulfide until the formation of the intermediate has ended,
for example after stirring for a number of hours at room
temperature.
[0333] Suitable bases for use in the process (C.beta.) are all
customary proton acceptors. Preference is given to using alkali
metal hydrides, alkali metal alkoxides, alkali metal or alkaline
earth metal carbonates or bicarbonates or nitrogen bases. Sodium
hydride, sodium methoxide, sodium hydroxide, calcium hydroxide,
potassium carbonate, sodium bicarbonate, triethylamine,
dibenzylamine, diisopropylethylamine, pyridine, quinoline,
diazabicyclooctane (DABCO), diazabicyclonone (DBN) and
diazabicycloundecene (DBU) may be mentioned by way of example.
[0334] Suitable diluents for use in this process are all customary
solvents.
[0335] Preference is given to using aromatic hydrocarbons, such as
benzene or toluene, alcohols, such as methanol, ethanol,
isopropanol or ethylene glycol, nitriles, such as acetonitrile,
ethers, such as tetrahydrofuran and dioxane, amides, such as
dimethylformamide, or other polar solvents, such as dimethyl
sulfoxide or sulfonane.
[0336] The further reaction with the alkyl halide of the formula
(VI) is preferably carried out at from 0 to 70.degree. C. and in
particular at from 20 to 50.degree. C. Here, at least an aquimolar
amount of alkyl halide is used.
[0337] The process is carried out at atmospheric pressure or under
elevated pressure, preferably at atmospheric pressure.
[0338] Work-up is again carried out by customary methods.
[0339] The process (D) according to the invention is characterized
in that compounds of the formula (I-a) are in each case reacted
with sulfonyl chlorides of the formula (VII), if appropriate in the
presence of a diluent and if appropriate in the presence of an acid
binder.
[0340] In preparation process (D), about 1 mol of sulfonyl chloride
of the formula (VII) is reacted per mole of starting material of
the formula (I-a), at from -20 to 150.degree. C., preferably from
20 to 70.degree. C.
[0341] The process (D) is preferably carried out in the presence of
a diluent.
[0342] Suitable diluents are all inert polar organic solvents, such
as ethers, esters, amides, nitriles, sulfones, sulfoxides or
halogenated hydrocarbons, such as methylene chloride.
[0343] Preference is given to using dimethyl sulfoxide,
tetrahydrofuran, ethyl acetate, dimethylformamide, methylene
chloride.
[0344] If, in a preferred embodiment, the enolate salt of the
compound (I-a) is prepared by adding strong deprotonating agents
(such as, for example, sodium hydride or potassium tert-butoxide),
the further addition of acid binders may be dispensed with.
[0345] If acid binders are used, these are customary inorganic or
organic bases, for example sodium hydride, sodium carbonate,
potassium carbonate, pyridine and triethylamine.
[0346] 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.
[0347] The process (E) according to the invention is characterized
in that compounds of the formula (I-a) are in each case reacted
with phosphorus compounds of the formula (VIII), if appropriate in
the presence of a diluent and if appropriate in the presence of an
acid binder.
[0348] In preparation process (E), to obtain compounds of the
formula (I-e), from 1 to 2, preferably from 1 to 1.3 mol of the
phosphorus compound of the formula (VIII) are reacted per mole of
the compound (I-a), at temperatures between 40.degree. C. and
150.degree. C., preferably between -10 and 110.degree. C.
[0349] The process (E) is preferably carried out in the presence of
a diluent.
[0350] Suitable diluents are all inert polar organic solvents, such
as ethers, esters, amides, nitriles, sulfides, sulfones,
sulfoxides, etc.
[0351] Preference is given to using acetonitrile, ethyl acetate,
dimethyl sulfoxide, tetrahydrofuran, dimethyl-formamide, methylene
chloride.
[0352] Suitable acid binders which are added, if appropriate, are
customary inorganic or organic bases, such as hydroxides,
carbonates or amines. Sodium hydroxide, sodium carbonate, potassium
carbonate, pyridine and triethylamine may be mentioned by way of
example.
[0353] The reaction can be carried out at atmospheric pressure or
under elevated pressure and is preferably carried out at
atmospheric pressure. Work-up is carried out by customary methods
of organic chemistry. The end products are preferably purified by
crystallization, chromatographic purification or by "insipient
distillation", i.e. the removal of the volatile components under
reduced pressure.
[0354] The process (F) is characterized in that compounds of the
formula (I-a) are in each case reacted with metal hydroxides or
metal alkoxides of the formula (IX) or amines of the formula (X),
if appropriate in the presence of a diluent.
[0355] Suitable diluents for use in the process (F) according to
the invention are, preferably, ethers, such as tetrahydrofuran,
dioxane, diethyl ether, or else alcohols, such as methanol,
ethanol, isopropanol, but also water. The process (F) according to
the invention is generally carried out under atmospheric pressure.
The reaction temperatures are generally between -20.degree. C. and
100.degree. C., preferably between 0.degree. C. and 50.degree.
C.
[0356] The process (G) according to the invention is characterized
in that compounds of the formula (I-a) are in each case reacted
with (G.alpha.) compounds of the formula (XI), if appropriate in
the presence of a diluent and if appropriate in the presence of a
catalyst, or (G.beta.) with compounds of the formula (XII), if
appropriate in the presence of a diluent and if appropriate in the
presence of an acid binder.
[0357] In preparation process (G.alpha.), about 1 mol of isocyanate
of the formula (XI) is reacted per mole of starting material of the
formula (I-a), at from 0 to 100.degree. C., preferably from 20 to
50.degree. C.
[0358] The process (G.alpha.) is preferably carried out in the
presence of a diluent.
[0359] Suitable diluents are all inert organic solvents, such as
ethers, esters, amides, nitriles, sulfones or sulfoxides.
[0360] If appropriate, catalysts may be added to promote the
reaction. Suitable for use as catalysts are, very advantageously,
organotin compounds, such as, for example, dibutyltin
dilaurate.
[0361] The process is preferably carried out at atmospheric
pressure.
[0362] In preparation process (G.beta.), about 1 mol of carbamoyl
chloride of the formula (XII) is reacted per mole of starting
material of the formula (I-a), at from 0 to 150.degree. C.,
preferably from 20 to 70.degree. C.
[0363] Suitable diluents which are added, if appropriate, are all
inert polar organic solvents, such as ethers, esters, amides,
sulfones, sulfoxides or halogenated hydrocarbons.
[0364] Preference is given to using dimethyl sulfoxide, ethyl
acetate, tetrahydrofuran, dimethylformamide or methylene
chloride.
[0365] If, in a preferred embodiment, the enolate salt of the
compound (I-a) is prepared by adding strong deprotonating agents
(such as, for example, sodium hydride or potassium tert-butoxide),
the further addition of acid binders may be dispensed with.
[0366] If acid binders are used, these are customary inorganic or
organic bases, for example sodium hydroxide, sodium carbonate,
potassium carbonate, triethylamine or pyridine.
[0367] The reaction can be carried out atmospheric pressure or
under elevated pressure and is preferably carried out at
atmospheric pressure. Work-up is carried out by customary
methods.
[0368] The active compounds are well tolerated by plants, have
favorable homeotherm toxicity and are environmentally friendly;
they are suitable for protecting plants and plant organs, for
increasing harvest yields, for improving the quality of the
harvested material and for controlling animal pests, in particular
insects, arachnids and nematodes encountered in agriculture, in
forests, in gardens and leisure facilities, in the protection of
stored products and materials and in the hygiene sector. They are
preferably used as crop protection agents. They are active against
normally sensitive and resistant species and against all or some
stages of development. The abovementioned pests include:
[0369] From the order of the Isopoda, for example, Oniscus asellus,
Armadillidium vulgare and Porcellio scaber.
[0370] From the order of the Diplopoda, for example, Blaniulus
guttulatus.
[0371] From the order of the Chilopoda, for example, Geophilus
carpophagus and Scutigera spp.
[0372] From the order of the Symphyla, for example, Scutigerella
immaculata.
[0373] From the order of the Thysanura, for example, Lepisma
saccharina.
[0374] From the order of the Collembola, for example, Onychiurus
armatus.
[0375] From the order of the Orthoptera, for example, Acheta
domesticus, Gryllotalpa spp., Locusta migratoria migratorioides,
Melanoplus spp. and Schistocerca gregaria.
[0376] From the order of the Blattaria, for example, Blatta
orientalis, Periplaneta americana, Leucophaea maderae and Blattella
germanica.
[0377] From the order of the Dermaptera, for example, Forficula
auricularia.
[0378] From the order of the Isoptera, for example, Reticulitermes
spp.
[0379] From the order of the Phthiraptera, for example, Pediculus
humanus corporis, Haematopinus spp., Linognathus spp., Trichodectes
spp., Damalinia spp.
[0380] From the order of the Thysanoptera, for example,
Hercinothrips femoralis, Thrips tabaci, Thrips palmi, Frankliniella
accidentalis.
[0381] From the order of the Heteroptera, for example, Eurygaster
spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius,
Rhodnius prolixus and Triatoma spp.
[0382] From the order of the Homoptera, for example, Aleurodes
brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis
gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae,
Aphis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Phylloxera
vastatrix, Pemphigus spp., Macrosiphum avenae, Myzus spp., Phorodon
humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus,
Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax
striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus
hederae, Pseudococcus spp. and Psylla spp.
[0383] From the order of the Lepidoptera, for example, Pectinophora
gossypiella, Bupalus piniarius, Chematobia brumata, Lithocolletis
blancardella, Hyponomeuta padella, Plutella xylostella, Malacosoma
neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix
thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp.,
Feltia spp., Earias insulana, Heliothis spp., Mamestra brassicae,
Panolis flammea, Spodoptera spp., Trichoplusia ni, Carpocapsa
pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia
kuehniella, Galleria mellonella, Tineola bisselliella, Tinea
pellionella, Hofmannophila pseudospretella, Cacoecia podana, Capua
reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona
magnanima, Tortrix viridana, Cnaphalocerus spp. and Oulema
oryzae.
[0384] From the order of the Coleoptera, for example, Anobium
punctatum, Rhizopertha dominica, Bruchidius obtectus,
Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni,
Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp.,
Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp.,
Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp.,
Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus
assimilis, Hypera postica, Dermestes spp., Trogoderma spp.,
Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus,
Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp.,
Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha
melolontha, Amphimallon solstitialis, Costelytra zealandica and
Lissorhoptrus oryzophilus.
[0385] From the order of the Hymenoptera, for example, Diprion
spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis and Vespa
spp.
[0386] From the order of the Diptera, for example, Aedes spp.,
Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp.,
Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia
spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomoxys
spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp.,
Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami,
Ceratitis capitata, Dacus oleae, Tipula paludosa, Hylemyia spp. and
Liriomyza spp.
[0387] From the order of the Siphonaptera, for example, Xenopsylla
cheopis and Ceratophyllus spp.
[0388] From the class of the Arachnida, for example, Scorpio
maurus, Latrodectus mactans, Acarus siro, Argas spp., Ornithodoros
spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta
oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp.,
Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp.,
Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus
spp., Tetranychus spp., Hemitarsonemus spp. and Brevipalpus
spp.
[0389] The plant-parasitic nematodes include, for example,
Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci,
Tylenchulus semipenetrans, Heterodera spp., Globodera spp.,
Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema
spp., Trichodorus spp. and Bursaphelenchus spp.
[0390] If appropriate, the compounds according to the invention may
also be used in certain concentrations or application rates to act
as herbicides and microbicides, for example as fungicides,
antimycotics and bactericides. If appropriate, they can also be
employed as intermediates or precursors for the synthesis of
further active compounds.
[0391] All plants and plant parts can be treated in accordance with
the invention. Plants are to be understood as meaning in the
present context all plants and plant populations such as desired
and undesired wild plants or crop plants (including naturally
occurring crop plants). Crop plants can be plants which can be
obtained by conventional plant breeding and optimization methods or
by biotechnological and recombinant methods or by combinations of
these methods, including the transgenic plants and inclusive of the
plant cultivars protectable or not protectable by plant breeders'
rights. Plant parts are to be understood as meaning all parts and
organs of plants above and below the ground, such as shoot, leaf,
flower and root, examples which may be mentioned being leaves,
needles, stalks, stems, flowers, fruit bodies, fruits, seeds,
roots, tubers and rhizomes. The plant parts also include harvested
material, and vegetative and generative propagation material, for
example cuttings, tubers, rhizomes, offsets and seeds.
[0392] The treatment according to the invention of the plants and
plant parts with the active compounds is carried out directly or by
allowing the compounds to act on their surroundings, habitat or
storage space by the customary treatment methods, for example by
immersion, spraying, evaporation, fogging, scattering, painting on,
injecting and, in the case of propagation material, in particular
in the case of seeds, also by applying one or more coats.
[0393] The active compounds can be converted into the customary
formulations such as solutions, emulsions, wettable powders,
suspensions, powders, dusts, pastes, soluble powders, granules,
suspension-emulsion concentrates, natural and synthetic materials
impregnated with active compound, and microencapsulations in
polymeric materials.
[0394] 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.
[0395] If the extender used is water, it is also possible, for
example, to use organic solvents as cosolvents. The following are
essentially suitable as liquid solvents: aromatics such as xylene,
toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated
aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or
methylene chloride, aliphatic hydrocarbons such as cyclohexane or
paraffins, for example mineral oil fractions, mineral and vegetable
oils, alcohols such as butanol or glycol and their ethers and
esters, ketones such as acetone, methyl ethyl ketone, methyl
isobutyl ketone or cyclohexanone, strongly polar solvents such as
dimethylformamide and dimethyl sulfoxide, or else water.
[0396] Suitable solid carriers are:
for example ammonium salts and ground natural minerals such as
kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite
or diatomaceous earth, and ground synthetic minerals such as highly
disperse silica, alumina and silicates; suitable solid carriers for
granules are: for example crushed and fractionated natural rocks
such as calcite, marble, pumice, sepiolite and dolomite, or else
synthetic granules of inorganic and organic meals, and granules of
organic material such as sawdust, coconut shells, maize cobs and
tobacco stalks; suitable emulsifiers and/or foam formers are: for
example nonionic and anionic emulsifiers such as polyoxyethylene
fatty acid esters, polyoxyethylene fatty alcohol ethers, for
example alkylaryl polyglycol ethers, alkylsulfonates, alkyl
sulfates, arylsulfonates, or else protein hydrolysates; suitable
dispersants are: for example lignosulfite waste liquors and
methylcellulose.
[0397] Tackifiers such as carboxymethylcellulose and natural and
synthetic polymers in the form of powders, granules or latices,
such as gum arabic, polyvinyl alcohol and polyvinyl acetate, or
else natural phospholipids such as cephalins and lecithins and
synthetic phospholipids can be used in the formulations. Other
additives can be mineral and vegetable oils.
[0398] It is possible to use colorants such as inorganic pigments,
for example iron oxide, titanium oxide and Prussian Blue, and
organic colorants such as alizarin colorants, azo colorants and
metal phthalocyanine colorants, and trace nutrients such as salts
of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
[0399] The formulations generally comprise between 0.1 and 95% by
weight of active compound, preferably between 0.5 and 90%.
[0400] The active compounds according to the invention, as such or
in their formulations, can also be used as a mixture with known
fungicides, bactericides, acaricides, nematicides or insecticides,
for example in order to widen the spectrum of action or to prevent
the development of resistances in this way. In many cases,
synergistic effects result, i.e. the activity of the mixture
exceeds the activity of the individual components.
[0401] Compounds which are suitable as mixing partners are, for
example, the following:
Fungicides:
[0402] 2-phenylphenol; 8-hydroxyquinoline sulfate;
acibenzolar-5-methyl; aldimorph; amidoflumet; ampropylfos;
ampropylfos-potassium; andoprim; anilazine; azaconazole;
azoxystrobin; benalaxyl; benodanil; benomyl;
benthiavalicarb-isopropyl; benzamacril; benzamacril-isobutyl;
bilanafos; binapacryl; biphenyl; bitertanol; blasticidin-S;
bromuconazole; bupirimate; buthiobate; butylamine; calcium
polysulfide; capsimycin; captafol; captan; carbendazim; carboxin;
carpropamid; carvone; chinomethionat; chlobenthiazone;
chlorfenazole; chloroneb; chlorothalonil; chlozolinate; clozylacon;
cyazofamid; cyflufenamid; cymoxanil; cyproconazole; cyprodinil;
cyprofuram; Dagger G; debacarb; dichlofluanid; dichlone;
dichlorophen; diclocymet; diclomezine; dicloran; diethofencarb;
difenoconazole; diflumetorim; dimethirimol; dimethomorph;
dimoxystrobin; diniconazole; diniconazole-M; dinocap;
diphenylamine; dipyrithione; ditalimfos; dithianon; dodine;
drazoxolon; edifenphos; epoxiconazole; ethaboxam; ethirimol;
etridiazole; famoxadone; fenamidone; fenapanil; fenarimol;
fenbuconazole; fenfuram; fenhexamid; fenitropan; fenoxanil;
fenpiclonil; fenpropidin; fenpropimorph; ferbam; fluazinam;
flubenzimine; fludioxonil; flumetover; flumorph; fluoromide;
fluoxastrobin; fluquinconazole; flurprimidol; flusilazole;
flusulfamide; flutolanil; flutriafol; folpet; fosetyl-Al;
fosetyl-sodium; fuberidazole; furalaxyl; furametpyr; furcarbanil;
furmecyclox; guazatine; hexachlorobenzene; hexaconazole;
hymexazole; imazalil; imibenconazole; iminoctadine triacetate;
iminoctadine tris(albesilate); iodocarb; ipconazole; iprobenfos;
iprodione; iprovalicarb; irumamycin; isoprothiolane; isovaledione;
kasugamycin; kresoxim-methyl; mancozeb; maneb; meferimzone;
mepanipyrim; mepronil; metalaxyl; metalaxyl-M; metconazole;
methasulfocarb; methfuroxam; metiram; metominostrobin; metsulfovax;
mildiomycin; myclobutanil; myclozolin; natamycin; nicobifen;
nitrothal-isopropyl; noviflumuron; nuarimol; ofurace; orysastrobin;
oxadixyl; oxolinic acid; oxpoconazole; oxycarboxin; oxyfenthiin;
paclobutrazole; pefurazoate; penconazole; pencycuron; phosdiphen;
phthalide; picoxystrobin; piperalin; polyoxins; polyoxorim;
probenazole; prochloraz; procymidone; propamocarb;
propanosine-sodium; propiconazole; propineb; proquinazid;
prothioconazole; pyraclostrobin; pyrazophos; pyrifenox;
pyrimethanil; pyroquilon; pyroxyfur; pyrrolenitrine; quinconazole;
quinoxyfen; quintozene; simeconazole; spiroxamine; sulfur;
tebuconazole; tecloftalam; tecnazene; tetcyclacis; tetraconazole;
thiabendazole; thicyofen; thifluzamide; thiophanate-methyl; thiram;
tioxymid; tolclofos-methyl; tolylfluanid; triadimefon; triadimenol;
triazbutil; triazoxide; tricyclamide; tricyclazole; tridemorph;
trifloxystrobin; triflumizole; triforine; triticonazole;
uniconazole; validamycin A; vinclozolin; zineb; ziram; zoxamide;
(2S)--N-[2-[4-[[3-(4-chlorophenyl)-2-propynyl]oxy]-3-methoxyphenyl]ethyl]-
-3-methyl-2-[(methylsulfonyl)amino]butanamide;
1-(1-naphthalenyl)-1H-pyrrole-2,5-dione;
2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine;
2-amino-4-methyl-N-phenyl-5-thiazolecarboxamide;
2-chloro-N-(2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl)-3-pyridinecarboxam-
ide; 3,4,5-trichloro-2,6-pyridinedicarbonitrile; actinovate;
cis-1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)cycloheptanol;
methyl
1-(2,3-dihydro-2,2-dimethyl-1H-inden-1-yl)-1H-imidazole-5-carboxylate;
monopotassium carbonate;
N-(6-methoxy-3-pyridinyl)cyclopropanecarboxamide;
N-butyl-8-(1,1-dimethylethyl)-1-oxaspiro[4.5]decane-3-amine; sodium
tetrathiocarbonate; and copper salts and preparations, such as
Bordeaux mixture; copper hydroxide; copper naphthenate; copper
oxychloride; copper sulfate; cufraneb; cuprous oxide; mancopper;
oxine-copper.
Bactericides:
[0403] bronopol, dichlorophen, nitrapyrin, nickel
dimethyldithiocarbamate, kasugamycin, octhilinone, furancarboxylic
acid, oxytetracyclin, probenazole, streptomycin, tecloftalam,
copper sulfate and other copper preparations.
Insecticides/Acaricides/Nematicides:
[0404] 1. Acetylcholine esterase (AChE) inhibitors [0405] 1.1
Carbamates, for example [0406] alanycarb, aldicarb, aldoxycarb,
allyxycarb, aminocarb, bendiocarb, benfuracarb, bufencarb,
butacarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran,
carbosulfan, cloethocarb, dimetilan, ethiofencarb, fenobucarb,
fenothiocarb, formetanate, furathiocarb, isoprocarb, metam-sodium,
methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, promecarb,
propoxur, thiodicarb, thiofanox, trimethacarb, XMC, xylylcarb
[0407] Triazamates [0408] 1.2 Organophosphates, for example [0409]
acephate, azamethiphos, azinphos (-methyl, -ethyl),
bromophos-ethyl, brom-fenvinfos (-methyl), butathiofos, cadusafos,
carbophenothion, chlorethoxyfos, chlorfenvinphos, chlormephos,
chlorpyrifos (-methyl/-ethyl), coumaphos, cyanofenphos, cyanophos,
chlorfenvinphos, demeton-S-methyl, demeton-S-methylsulfone,
dialifos, diazinon, dichlofenthion, dichlorvos/DDVP, dicrotophos,
dimethoate, dimethylvinphos, dioxabenzofos, disulfoton, EPN,
ethion, ethoprophos, etrimfos, famphur, fenamiphos, fenitrothion,
fensulfothion, fenthion, flupyrazofos, fonofos, formothion,
fosmethilan, fosthiazate, heptenophos, iodofenphos, iprobenfos,
isazofos, isofenphos, isopropyl O-salicylate, isoxathion,
malathion, mecarbam, methacrifos, methamidophos, methidathion,
mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl,
parathion (-methyl/-ethyl), phenthoate, phorate, phosalone,
phosmet, phosphamidon, phosphocarb, phoxim, pirimiphos
(-methyl/-ethyl), profenofos, propaphos, propetamphos, prothiofos,
prothoate, pyraclofos, pyridaphenthion, pyridathion, quinalphos,
sebufos, sulfotep, sulprofos, tebupirimfos, temephos, terbufos,
tetrachlorvinphos, thiometon, triazophos, triclorfon, vamidothion
[0410] 2. Sodium channel modulators/voltage-dependent sodium
channel blockers [0411] 2.1 Pyrethroids, for example [0412]
acrinathrin, allethrin (d-cis-trans, d-trans), beta-cyfluthrin,
bifenthrin, bioallethrin, bioallethrin-S cyclopentyl isomer,
bioethanomethrin, biopermethrin, bioresmethrin, chlovaporthrin,
cis-cypermethrin, cis-resmethrin, cis-permethrin, clocythrin,
cycloprothrin, cyfluthrin, cyhalothrin, cypermethrin (alpha-,
beta-, theta-, zeta-), cyphenothrin, deltamethrin, empenthrin (1R
isomer), esfenvalerate, etofenprox, fenfluthrin, fenpropathrin,
fenpyrithrin, fenvalerate, flubrocythrinate, flucythrinate,
flufenprox, flumethrin, fluvalinate, fubfenprox, gamma-cyhalothrin,
imiprothrin, kadethrin, lambda-cyhalothrin, metofluthrin,
permethrin (cis-, trans-), phenothrin (IR trans-isomer),
prallethrin, profluthrin, protrifenbute, pyresmethrin, resmethrin,
RU 15525, silafluofen, tau-fluvalinate, tefluthrin, terallethrin,
tetramethrin (1R isomer), tralomethrin, transfluthrin, ZXI 8901,
pyrethrins (pyrethrum) [0413] DDT [0414] 2.2 Oxadiazines, for
example indoxacarb [0415] 3. Acetylcholine receptor
agonists/antagonists [0416] 3.1 Chloronicotinyls, for example
[0417] acetamiprid, clothianidin, dinotefuran, imidacloprid,
nitenpyram, nithiazine, thiacloprid, thiamethoxam [0418] 3.2
Nicotine, bensultap, cartap [0419] 4. Acetylcholine receptor
modulators [0420] 4.1 Spinosyns, for example spinosad [0421] 5.
GABA-controlled chloride channel antagonists [0422] 5.1 Cyclodiene
organochlorines, for example [0423] camphechlor, chlordane,
endosulfan, gamma-HCH, HCH, heptachlor, lindane, methoxychlor
[0424] 5.2 Fiproles, for example [0425] acetoprole, ethiprole,
fipronil, vaniliprole [0426] 6. Chloride channel activators [0427]
6.1 Mectins, for example [0428] avermectin, emamectin,
emamectin-benzoate, ivermectin, milbemycin [0429] 7. Juvenile
hormone mimetics, for example [0430] diofenolan, epofenonane,
fenoxycarb, hydroprene, kinoprene, methoprene, pyriproxifen,
triprene [0431] 8. Ecdyson agonists/disruptors [0432] 8.1
Diacylhydrazines, for example [0433] chromafenozide, halofenozide,
methoxyfenozide, tebufenozide [0434] 9. Chitin biosynthesis
inhibitors [0435] 9.1 Benzoylureas, for example [0436]
bistrifluoron, chlofluazuron, diflubenzuron, fluazuron,
flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron,
noviflumuron, penfluoron, teflubenzuron, triflumuron [0437] 9.2
Buprofezin [0438] 9.3 Cyromazine [0439] 10. Oxidative
phosphorylation inhibitors, ATP disruptors [0440] 10.1
Diafenthiuron [0441] 10.2 Organotins, for example azocyclotin,
cyhexatin, fenbutatin-oxide [0442] 11. Oxidative phosphorylation
decouplers acting by interrupting the H-proton gradient [0443] 11.1
Pyrroles, for example chlorfenapyr [0444] 11.2 Dinitrophenols, for
example binapacyrl, dinobuton, dinocap, DNOC [0445] 12. Site-I
electron transport inhibitors [0446] 12.1 METIs, for example
fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad,
tolfenpyrad [0447] 12.2 Hydramethylnon [0448] 12.3 Dicofol [0449]
13. Site-II electron transport inhibitors [0450] Rotenone [0451]
14. Site-III electron transport inhibitors [0452] Acequinocyl,
fluacrypyrim [0453] 15. Microbial disruptors of the insect gut
membrane [0454] Bacillus thuringiensis strains [0455] 16. Fat
synthesis inhibitors [0456] Tetronic acids, for example [0457]
spirodiclofen, spiromesifen [0458] Tetramic acids, for example
[0459] spirotetramat [0460] 17. Carboxamides, for example
flonicamid [0461] 18. Octopaminergic agonists, for example amitraz
[0462] 19. Inhibitors of magnesium-stimulated ATPase, for example
propargite [0463] 20. BDCAs, for example
N2-[1,1-dimethyl-2-(methylsulfonyl)ethyl]-3-iodo-N1-[2-methyl-4-[1,2,2,2--
tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]-1,2-benzenedicarboxamide
(CAS-Reg.-No.: 272451-65-7) [0464] 21. Nereistoxin analogs, for
example thiocyclam hydrogen oxalate, thiosultap-sodium [0465] 22.
Biologicals, hormones or pheromones, for example [0466]
azadirachtin, Bacillus spec., Beauveria spec., codlemone,
Metarrhizium spec., Paecilomyces spec., thuringiensin, Verticillium
spec. [0467] 23. Active compounds with unknown or unspecific
mechanisms of action [0468] 23.1 Fumigants, for example [0469]
aluminum phosphide, methyl bromide, sulfuryl fluoride [0470] 23.2
Selective antifeedants, for example [0471] cryolite, flonicamid,
pymetrozine [0472] 23.3 Mite growth inhibitors, for example [0473]
clofentezine, etoxazole, hexythiazox [0474] 23.4 Amidoflumet,
benclothiaz, benzoximate, bifenazate, bromopropylate, buprofezin,
quinomethionate, chlordimeform, chlorobenzilate, chloropicrin,
clothiazoben, cycloprene, dicyclanil, fenoxacrim, fentrifanil,
flubenzimine, flufenerim, flutenzin, gossyplure, hydramethylnone,
japonilure, metoxadiazone, petroleum, piperonyl butoxide, potassium
oleate, pyridalyl, sulfluramid, tetradifon, tetrasul, triarathene,
verbutin, and also products which comprise insecticidal plant
extracts, nematodes, fungi or viruses.
[0475] A mixture with other known active compounds, such as
herbicides, or with fertilizers and growth regulators, safeners
and/or semiochemicals is also possible.
[0476] When used as insecticides in their commercially available
formulations and in the use forms prepared with these formulations,
the active compounds according to the invention can furthermore be
present in the form of a mixture with synergists. Synergists are
compounds by which the activity of the active compounds is
increased without it being necessary for the synergist added to be
active itself.
[0477] When used as insecticides in their commercially available
formulations and in the use forms prepared with these formulations,
the active compounds according to the invention can furthermore be
present in the form of a mixture with inhibitors which reduce the
degradation of the active compound after application in the habitat
of the plant, on the surface of parts of plants or in plant
tissues.
[0478] The active compound content of the use forms prepared from
the commercially available formulations can vary within broad
ranges. The active compound concentration of the use forms can be
from 0.0000001 up to 95% by weight of active compound, preferably
between 0.0001 and 1% by weight.
[0479] They are applied in a customary manner adapted to suit the
use forms.
[0480] When used against hygiene pests and pests of stored
products, the active compound is distinguished by excellent
residual action on wood and clay as well as good stability to
alkali on limed substrates.
[0481] As already mentioned above, it is possible to treat all
plants and their parts in accordance with the invention. In a
preferred embodiment, wild plant species or plant varieties and
plant cultivars which have been obtained by traditional biological
breeding methods, such as hybridization or protoplast fusion, and
the parts of these varieties and cultivars are treated. In a
further preferred embodiment, transgenic plants and plant cultivars
which have been obtained by recombinant methods, if appropriate in
combination with conventional methods (genetic modified organisms),
and their parts are treated. The term "parts" or "parts of plants"
or "plant parts" has been explained above.
[0482] Plants which are treated particularly preferably in
accordance with the invention are those of the plant cultivars
which are in each case commercially available or in use. Plant
cultivars are understood as meaning plants with new traits which
have been bred either by conventional breeding, by mutagenesis or
by recombinant DNA techniques. They may take the form of cultivars,
biotypes and genotypes.
[0483] Depending on the plant species or plant cultivars, their
location and growth conditions (soils, climate, vegetation period,
nutrition), the treatment according to the invention may also
result in superadditive ("synergistic") effects. Thus, for example,
reduced application rates and/or a widened activity spectrum and/or
an increase in the activity of the substances and compositions
which can be used in accordance with the invention, better plant
growth, increased tolerance to high or low temperatures, increased
tolerance to drought or to salinity in the water or soil, increased
flowering performance, facilitated harvesting, accelerated
maturation, higher yields, higher quality and/or better nutritional
value of the harvested products, better storage characteristics
and/or processability of the harvested products are possible which
exceed the effects which were actually to be expected.
[0484] The preferred transgenic plants or plant cultivars (those
obtained by recombinant methods) to be treated in accordance with
the invention include all those plants which, owing to the process
of recombinant modification, were given genetic material which
confers particular, advantageous, valuable traits to these plants.
Examples of such properties are better plant growth, increased
tolerance to high or low temperatures, increased tolerance to
drought or to salinity in the water or soil, increased flowering
performance, facilitated harvesting, accelerated maturation, higher
yields, higher quality and/or higher nutritional value of the
harvested products, better storage characteristics and/or better
processability of the harvested products. Further examples of such
traits, examples which must be mentioned especially, are better
defense of the plants against animal and microbial pests, such as
against insects, mites, phytopathogenic fungi, bacteria and/or
viruses and an increased tolerance of the plants to certain
herbicidal active compounds. Examples of transgenic plants which
may be mentioned are the important crop plants, such as cereals
(wheat, rice), maize, soybeans, potato, cotton, tobacco, oilseed
rape and fruit plants (with the fruits apples, pears, citrus fruits
and grapes), with particular emphasis on maize, soybeans, potatoes,
cotton, tobacco, and oilseed rape. Traits which are especially
emphasized are the increased defense of the plants against insects,
arachnids, nematodes and slugs and snails, owing to toxins being
formed in the plants, in particular toxins which are generated in
the plants by the genetic material of Bacillus thuringiensis (for
example by the genes CryIA(a), CryIA(b), CryIA(c), CryIIA, CryIIIA,
CryIIIB2, Cry9c Cry2Ab, Cry3Bb and CryIF and their combinations;
hereinbelow "Bt plants"). Other traits which are particularly
emphasized are the increased defense of plants against fungi,
bacteria and viruses by the systemic acquired resistance (SAR),
systemin, phytoalexins, elicitors and resistance genes and
correspondingly expressed proteins and toxins. Other traits which
are especially emphasized are the increased tolerance of the plants
to certain herbicidal active compounds, for example imidazolinones,
sulfonylureas, glyphosate or phosphinotricin (for example "PAT"
gene). The genes which confer the desired traits in each case may
also be present in the transgenic plants in combination with one
another. Examples of "Bt plants" which may be mentioned are maize
cultivars, cotton cultivars, soybean cultivars and potato cultivars
which are commercially available under the trade names YIELD
GARD.RTM. (for example maize, cotton, soybeans), KnockOut.RTM. (for
example maize), StarLink.RTM. (for example maize), Bollgard.RTM.
(cotton), Nucotn.RTM. (cotton) and NewLeaf.RTM. (potato). Examples
of herbicide-tolerant plants which may be mentioned are maize
cultivars, cotton cultivars and soybean cultivars which are
commercially available under the trade names Roundup Ready.RTM.
(tolerance to glyphosate, for example maize, cotton, soybean),
Liberty Link.RTM. (tolerance to phosphinotricin, for example
oilseed rape), IMI.RTM. (tolerance to imidazolinones) and STS.RTM.
(tolerance to sulfonylureas, for example maize).
Herbicide-resistant plants (plants bred in a conventional manner
for herbicide tolerance) which may be mentioned also include the
varieties commercially available under the name Clearfield.RTM.
(for example maize). Naturally, these statements also apply to
plant cultivars having these genetic traits or genetic traits still
to be developed, which plant cultivars will be developed and/or
marketed in the future.
[0485] The plants listed can be treated particularly advantageously
according to the invention with the compounds of the general
formula I or the active compound mixtures according to the
invention. The preferred ranges stated above for the active
compounds and mixtures also apply to the treatment of these plants.
Particular emphasis may be given to the treatment of plants with
the compounds or mixtures specifically mentioned in the present
text.
[0486] The active compounds according to the invention are not only
active against plant, hygiene and stored-product pests, but also,
in the veterinary medicine sector, against animal parasites
(ectoparasites), such as ixodid ticks, argasid ticks, scab mites,
trombi-culid mites, flies (stinging and sucking), parasitic fly
larvae, lice, hair lice, bird lice and fleas. These parasites
include:
[0487] From the order of the Anoplurida, for example, Haematopinus
spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes
spp.
[0488] From the order of the Mallophagida and the sub-orders
Amblycerina and Ischnocerina, for example, Trimenopon spp., Menopon
spp., Trinoton spp., Bovicola spp., Wemeckiella spp., Lepikentron
spp., Damalina spp., Trichodectes spp., Felicola spp.
[0489] From the order of the Diptera and the sub-orders
Nematocerina and Brachycerina, for example, Aedes spp., Anopheles
spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp.,
Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp.,
Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp.,
Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia
spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp.,
Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp.,
Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp.,
Lipoptena spp. and Melophagus spp.
[0490] From the order of the Siphonapterida, for example, Pulex
spp., Ctenocephalides spp., Xenopyslla spp. and Ceratophyllus
spp.
[0491] From the order of the Heteropterida, for example, Cimex
spp., Triatoma spp., Rhodnius spp. and Panstrongylus spp.
[0492] From the order of the Blattarida, for example, Blatta
orientalis, Periplaneta americana, Blattela germanica and Supella
spp.
[0493] From the sub-class of the Acaria (Acarina) and the orders of
the Meta- and Mesostigmata, for example, Argas spp., Ornithodorus
spp., Otobius spp., Ixodes spp., Amblyomma spp., Boophilus spp.,
Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus
spp., Dermanyssus spp., Raillietia spp., Pneumonyssus spp.,
Sternostoma spp. and Varroa spp.
[0494] From the order of the Actinedida (Prostigmata) and Acaridida
(Astigmata), for example, Acarapis spp., Cheyletiella spp.,
Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp.,
Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp.,
Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes
spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres
spp., Knemidocoptes spp., Cytodites spp. and Laminosioptes spp.
[0495] The active compounds of the formula (I) according to the
invention are also suitable for controlling arthropods which attack
agricultural livestock, such as, for example, cattle, sheep, goats,
horses, pigs, donkeys, camels, buffaloes, rabbits, chickens,
turkeys, ducks, geese, honeybees, other domestic animals, such as,
for example, dogs, cats, cage birds, aquarium fish, and so-called
experimental animals, such as, for example, hamsters, guinea-pigs,
rats and mice. By combating these arthropods, it is intended to
reduce deaths and decreased performances (in meat, milk, wool,
hides, eggs, honey and the like), so that more economical and
simpler animal keeping is made possible by using the active
compounds according to the invention.
[0496] In the veterinary sector, the active compounds according to
the invention are used in a known manner by enteral administration,
for example in the form of tablets, capsules, drinks, drenches,
granules, pastes, boli, the feed-through method, suppositories, by
parenteral administration, such as, for example, by means of
injections (intramuscular, subcutaneous, intravenous,
intraperitoneal and the like), implants, by nasal application, by
dermal administration, for example in the form of dipping or
bathing, spraying, pouring-on and spotting-on, washing, dusting,
and with the aid of shaped articles which comprise active compound,
such as collars, ear tags, tail marks, limb bands, halters, marking
devices and the like.
[0497] When administered to livestock, poultry, domestic animals
and the like, the active compounds of the formula (I) can be used
as formulations (for example powders, emulsions, flowables) which
comprise the active compounds in an amount of 1 to 80% by weight,
either directly or after dilution by a factor of 100 to 10 000, or
they may be used in the form of a chemical bath.
[0498] Furthermore, it has been found that the compounds according
to the invention have a potent insecticidal action against insects
which destroy industrial materials.
[0499] The following insects may be mentioned by way of example and
as being preferred, but without any limitation:
[0500] Beetles, such as
[0501] Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum,
Xestobium rufovillosum, Ptilinus pecticornis, Dendrobium pertinex,
Emobius mollis, Priobium carpini, Lyctus brunneus, Lyctus
africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens,
Trogoxylon aequale, Minthes rugicollis, Xyleborus spec.,
Tryptodendron spec., Apate monachus, Bostrychus capucins,
Heterobostrychus brunneus, Sinoxylon spec., Dinoderus minutus.
[0502] Dermapterans, such as
[0503] Sirex juvencus, Urocerus gigas, Urocerus gigas taignus,
Urocerus augur.
[0504] Termites, such as
[0505] Kalotermes flavicollis, Cryptotermes brevis, Heterotermes
indicola, Reticulitermes flavipes, Reticulitermes santonensis,
Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis
nevadensis, Coptotermes formosanus.
[0506] Bristletails, such as Lepisma saccharina.
[0507] Industrial materials are to be understood as meaning, in the
present context, non-live materials, such as, preferably, synthetic
materials, glues, sizes, paper and board, leather, wood and timber
products, and paint.
[0508] The materials to be very particularly preferably protected
against attack by insects are wood and timber products.
[0509] Wood and timber products which can be protected by the
composition according to the invention or mixtures comprising such
a composition are to be understood as meaning, for example:
construction timber, wooden beams, railway sleepers, bridge
components, jetties, wooden vehicles, boxes, pallets, containers,
telephone poles, wood cladding, windows and doors made of wood,
plywood, particle board, joiner's articles, or wood products which,
quite generally, are used in the construction of houses or in
joinery.
[0510] The active compounds can be used as such, in the form of
concentrates or generally customary formulations, such as powders,
granules, solutions, suspensions, emulsions or pastes.
[0511] The formulations mentioned can be prepared in a manner known
per se, for example by mixing the active compounds with at least
one solvent or diluent, emulsifier, dispersant and/or binder or
fixative, water repellent, if appropriate desiccants and UV
stabilizers and, if appropriate, colorants and pigments and other
processing auxiliaries.
[0512] The insecticidal compositions or concentrates used for the
protection of wood and wooden materials comprise the active
compound according to the invention in a concentration of 0.0001 to
95% by weight, in particular 0.001 to 60% by weight.
[0513] The amount of the compositions or concentrates employed
depends on the species and the occurrence of the insects and on the
medium. The optimum rate of application can be determined upon use
in each case by a test series. However, in general, it suffices to
employ 0.0001 to 20% by weight, preferably 0.001 to 10% by weight,
of the active compound, based on the material to be protected.
[0514] The solvent and/or diluent used is an organochemical solvent
or solvent mixture and/or an oily or oil-type organochemical
solvent or solvent mixture of low volatility and/or a polar
organochemical solvent or solvent mixture and/or water and, if
appropriate, an emulsifier and/or wetting agent.
[0515] Organochemical solvents which are preferably employed are
oily or oil-type solvents having an evaporation number of above 35
and a flashpoint of above 30.degree. C., preferably above
45.degree. C. Substances which are used as such oily and oil-type
solvents which have low volatility and are insoluble in water are
suitable mineral oils or their aromatic fractions, or
mineral-oil-containing solvent mixtures, preferably white spirit,
petroleum and/or alkylbenzene.
[0516] Substances which are advantageously used are mineral oils
with a boiling range of 170 to 220.degree. C., white spirit with a
boiling range of 170 to 220.degree. C., spindle oil with a boiling
range of 250 to 350.degree. C., petroleum or aromatics of boiling
range 160 to 280.degree. C., essence of terpentine and the
like.
[0517] In a preferred embodiment, liquid aliphatic hydrocarbons
with a boiling range of 180 to 210.degree. C. or high-boiling
mixtures of aromatic and aliphatic hydrocarbons with a boiling
range of 180 to 220.degree. C. and/or spindle oil and/or
monochloronaphthalene, preferably .alpha.-monochloronaphthalene,
are used.
[0518] The organic oily or oil-type solvents of low volatility
having an evaporation number of above 35 and a flashpoint of above
30.degree. C., preferably above 45.degree. C., can be partially
replaced by organochemical solvents of high or medium volatility,
with the proviso that the solvent mixture also has an evaporation
number of above 35 and a flashpoint of above 30.degree. C.,
preferably above 45.degree. C., and that the insecticide/fungicide
mixture is soluble or emulsifiable in this solvent mixture.
[0519] In a preferred embodiment, part of the organochemical
solvent or solvent mixture or an aliphatic polar organochemical
solvent or solvent mixture is replaced. Substances which are
preferably used are aliphatic organochemical solvents having
hydroxyl and/or ester and/or ether groups, such as, for example,
glycol ethers, esters and the like.
[0520] The organochemical binders used within the scope of the
present invention are the synthetic resins and/or binding drying
oils which are known per se and can be diluted with water and/or
are soluble or dispersible or emulsifiable in the organochemical
solvents employed, in particular binders composed of, or
comprising, an acrylate resin, a vinyl resin, for example polyvinyl
acetate, polyester resin, polycondensation or polyaddition resin,
polyurethane resin, alkyd resin or modified alkyd resin, phenol
resin, hydrocarbon resin, such as indene/coumarone resin, silicone
resin, drying vegetable and/or drying oils and/or physically drying
binders based on a natural and/or synthetic resin.
[0521] The synthetic resin used as the binder can be employed in
the form of an emulsion, dispersion or solution. Up to 10% by
weight of bitumen or bituminous substances can also be used as
binders. In addition, colorants, pigments, water repellents,
odor-masking substances and inhibitors or anticorrosives known per
se and the like can also be employed.
[0522] The composition or the concentrate preferably comprises, in
accordance with the invention, at least one alkyd resin or modified
alkyd resin and/or a drying vegetable oil as the organochemical
binder. Preferably used according to the invention are alkyd resins
with an oil content of over 45% by weight, preferably 50 to 68% by
weight.
[0523] All or some of the abovementioned binder can be replaced by
a fixative (mixture) or a plasticizer (mixture). These additives
are intended to prevent volatilization of the active compounds and
crystallization or precipitation. They preferably replace 0.01 to
30% of the binder (based on 100% of binder employed).
[0524] The plasticizers are from the chemical classes of the
phthalic esters, such as dibutyl phthalate, dioctyl phthalate or
benzyl butyl phthalate, the phosphoric esters, such as tributyl
phosphate, the adipic esters, such as di(2-ethylhexyl) adipate, the
stearates, such as butyl stearate or amyl stearate, the oleates,
such as butyl oleate, the glycerol ethers or relatively
high-molecular-weight glycol ethers, glycerol esters and
p-toluenesulfonic esters.
[0525] Fixatives are chemically based on polyvinyl alkyl ethers,
such as, for example, polyvinyl methyl ether, or ketones, such as
benzophenone or ethylenebenzophenone.
[0526] Particularly suitable as a solvent or diluent is also water,
if appropriate as a mixture with one or more of the abovementioned
organochemical solvents or diluents, emulsifiers and
dispersants.
[0527] Particularly effective protection of wood is achieved by
large-scale industrial impregnation processes, for example vacuum,
double-vacuum or pressure processes.
[0528] If appropriate, the ready-to-use compositions can
additionally comprise other insecticides and, if appropriate,
additionally one or more fungicides.
[0529] Suitable additional components which may be admixed are,
preferably, the insecticides and fungicides mentioned in WO 94/29
268. The compounds mentioned in that document are expressly part of
the present application.
[0530] Very particularly preferred components which may be admixed
are insecticides, such as chlorpyriphos, phoxim, silafluofin,
alphamethrin, cyfluthrin, cypermethrin, deltamethrin, permethrin,
imidacloprid, NI-25, flufenoxuron, hexaflumuron, transfluthrin,
thiacloprid, methoxyphenoxid, triflumuron, chlothianidin, spinosad,
tefluthrin,
and fungicides, such as epoxyconazole, hexaconazole, azaconazole,
propiconazole, tebuconazole, cyproconazole, metconazole, imazalil,
dichlorfluanid, tolylfluanid, 3-iodo-2-propynylbutyl carbamate,
N-octyl-isothiazolin-3-one and
4,5-dichloro-N-octylisothiazolin-3-one.
[0531] The compounds according to the invention can at the same
time be employed for protecting objects which come into contact
with salt water or brackish water, in particular hulls, screens,
nets, buildings, moorings and signaling systems, against
fouling.
[0532] Fouling by sessile Oligochaeta, such as Serpulidae, and by
shells and species from the Ledamorpha group (goose barnacles),
such as various Lepas and Scalpellum species, or by species from
the Balanomorpha group (acorn barnacles), such as Balanus or
Pollicipes species, increases the frictional drag of ships and, as
a consequence, leads to a marked increase in operation costs owing
to higher energy consumption and additionally frequent residence in
the dry dock.
[0533] Apart from fouling by algae, for example Ectocarpus sp. and
Ceramium sp., fouling by sessile Entomostraka groups, which come
under the generic term Cirripedia (cirriped crustaceans), is of
particular importance.
[0534] Surprisingly, it has now been found that the compounds
according to the invention, alone or in combination with other
active compounds, have an outstanding antifouling action.
[0535] Using the compounds according to the invention, alone or in
combination with other active compounds, allows the use of heavy
metals such as, for example, in bis(trialkyltin) sulfides,
tri-n-butyltin laurate, tri-n-butyltin chloride, copper(I) oxide,
triethyltin chloride, tri-n-butyl-(2-phenyl-4-chlorophenoxy)tin,
tributyltin oxide, molybdenum disulfide, antimony oxide, polymeric
butyl titanate, phenyl-(bispyridine)-bismuth chloride,
tri-n-butyltin fluoride, manganese ethylenebisthio-carbamate, zinc
dimethyldithiocarbamate, zinc ethylenebisthiocarbamate, zinc salts
and copper salts of 2-pyridinethiol 1-oxide,
bisdimethyldithiocarbamoylzinc ethylenebisthiocarbamate, zinc
oxide, copper(I) ethylenebisdithiocarbamate, copper thiocyanate,
copper naphthenate and tri-butyltin halides to be dispensed with,
or the concentration of these compounds to be substantially
reduced.
[0536] If appropriate, the ready-to-use antifouling paints can
additionally comprise other active compounds, preferably algicides,
fungicides, herbicides, molluscicides, or other antifouling active
compounds.
[0537] Preferably suitable components in combination with the
antifouling compositions according to the invention are:
algicides such as
2-tert-butylamino-4-cyclopropylamino-6-methylthio-1,3,5-triazine,
dichlorophen, diuron, endothal, fentin acetate, isoproturon,
methabenzthiazuron, oxyfluorfen, quinoclamine and terbutryn;
fungicides such as benzo[b]thiophenecarboxylic acid cyclohexylamide
S,S-dioxide, dichlofluanid, fluorfolpet, 3-iodo-2-propynyl
butylcarbamate, tolylfluanid and azoles such as azaconazole,
cyproconazole, epoxyconazole, hexaconazole, metconazole,
propiconazole and tebuconazole; molluscicides such as fentin
acetate, metaldehyde, methiocarb, niclosamid, thiodicarb and
trimethacarb; Fe chelates; or conventional antifouling active
compounds such as 4,5-dichloro-2-octyl-4-isothiazolin-3-one,
diiodomethylparatryl sulfone,
2-(N,N-dimethyl-thiocarbamoylthio)-5-nitrothiazyl, potassium,
copper, sodium and zinc salts of 2-pyridinethiol 1-oxide,
pyridine/triphenylborane, tetrabutyldistannoxane,
2,3,5,6-tetrachloro-4-(methylsulfonyl)-pyridine,
2,4,5,6-tetrachloroisophthalonitrile, tetramethylthiuram disulfide
and 2,4,6-trichlorophenylmaleimide.
[0538] The antifouling compositions used comprise the active
compound according to the invention of the compounds according to
the invention in a concentration of 0.001 to 50% by weight, in
particular 0.01 to 20% by weight.
[0539] Moreover, the antifouling compositions according to the
invention comprise the customary components such as, for example,
those described in Ungerer, Chem. Ind. 1985, 37, 730-732 and
Williams, Antifouling Marine Coatings, Noyes, Park Ridge, 1973.
[0540] Besides the algicidal, fungicidal, molluscicidal active
compounds and insecticidal active compounds according to the
invention, antifouling paints comprise, in particular, binders.
[0541] Examples of recognized binders are polyvinyl chloride in a
solvent system, chlorinated rubber in a solvent system, acrylic
resins in a solvent system, in particular in an aqueous system,
vinyl chloride/vinyl acetate copolymer systems in the form of
aqueous dispersions or in the form of organic solvent systems,
butadiene/styrene/acrylonitrile rubbers, drying oils such as
linseed oil, resin esters or modified hardened resins in
combination with tar or bitumens, asphalt and epoxy compounds,
small amounts of chlorine rubber, chlorinated polypropylene and
vinyl resins.
[0542] If appropriate, paints also comprise inorganic pigments,
organic pigments or colorants which are preferably insoluble in
salt water. Paints may furthermore comprise materials such as rosin
to allow controlled release of the active compounds. Furthermore,
the paints may comprise plasticizers, modifiers which affect the
rheological properties and other conventional constituents. The
compounds according to the invention or the abovementioned mixtures
may also be incorporated into self-polishing antifouling
systems.
[0543] The active compounds are also suitable for controlling
animal pests, in particular insects, arachnids and mites, which are
found in enclosed spaces such as, for example, dwellings, factory
halls, offices, vehicle cabins and the like. They can be employed
in domestic insecticide products for controlling these pests alone
or in combination with other active compounds and auxiliaries. They
are active against sensitive and resistant species and against all
development stages. These pests include:
[0544] From the order of the Scorpionidea, for example, Buthus
occitanus.
[0545] From the order of the Acarina, for example, Argas persicus,
Argas reflexus, Bryobia ssp., Dermanyssus gallinae, Glyciphagus
domesticus, Ornithodorus moubat, Rhipicephalus sanguineus,
Trombicula alfreddugesi, Neutrombicula autumnalis, Dermatophagoides
pteronissimus, Dermatophagoides forinae.
[0546] From the order of the Araneae, for example, Aviculariidae,
Araneidae.
[0547] From the order of the Opiliones, for example,
Pseudoscorpiones chelifer, Pseudoscorpiones cheiridium, Opiliones
phalangium.
[0548] From the order of the Isopoda, for example, Oniscus asellus,
Porcellio scaber.
[0549] From the order of the Diplopoda, for example, Blaniulus
guttulatus, Polydesmus spp.
[0550] From the order of the Chilopoda, for example, Geophilus
spp.
[0551] From the order of the Zygentoma, for example, Ctenolepisma
spp., Lepisma saccharina, Lepismodes inquilinus.
[0552] From the order of the Blattaria, for example, Blatta
orientalies, Blattella germanica, Blattella asahinai, Leucophaea
maderae, Panchlora spp., Parcoblatta spp., Periplaneta
australasiae, Periplaneta americana, Periplaneta brunnea,
Periplaneta fuliginosa, Supella longipalpa.
[0553] From the order of the Saltatoria, for example, Acheta
domesticus.
[0554] From the order of the Dermaptera, for example, Forficula
auricularia.
[0555] From the order of the Isoptera, for example, Kalotermes
spp., Reticulitermes spp.
[0556] From the order of the Psocoptera, for example, Lepinatus
spp., Liposcelis spp.
[0557] From the order of the Coleptera, for example, Anthrenus
spp., Attagenus spp., Dermestes spp., Latheticus oryzae, Necrobia
spp., Ptinus spp., Rhizopertha dominica, Sitophilus granarius,
Sitophilus oryzae, Sitophilus zeamais, Stegobium paniceum.
[0558] From the order of the Diptera, for example, Aedes aegypti,
Aedes albopictus, Aedes taeniorhynchus, Anopheles spp., Calliphora
erythrocephala, Chrysozona pluvialis, Culex quinquefasciatus, Culex
pipiens, Culex tarsalis, Drosophila spp., Fannia canicularis, Musca
domestica, Phlebotomus spp., Sarcophaga carnaria, Simulium spp.,
Stomoxys calcitrans, Tipula paludosa.
[0559] From the order of the Lepidoptera, for example, Achroia
grisella, Galleria mellonella, Plodia interpunctella, Tinea
cloacella, Tinea pellionella, Tineola bisselliella.
[0560] From the order of the Siphonaptera, for example,
Ctenocephalides canis, Ctenocephalides felis, Pulex irritans, Tunga
penetrans, Xenopsylla cheopis.
[0561] From the order of the Hymenoptera, for example, Camponotus
herculeanus, Lasius fuliginosus, Lasius niger, Lasius umbratus,
Monomorium pharaonis, Paravespula spp., Tetramorium caespitum.
[0562] From the order of the Anoplura, for example, Pediculus
humanus capitis, Pediculus humanus corporis, Phthirus pubis.
[0563] From the order of the Heteroptera, for example, Cimex
hemipterus, Cimex lectularius, Rhodinus prolixus, Triatoma
infestans.
[0564] They are used in the household insecticides sector alone or
in combination with other suitable active compounds such as
phosphoric esters, carbamates, pyrethroids, neonicotinoids, growth
regulators or active compounds from other known classes of
insecticides.
[0565] They are used in aerosols, pressure-free spray products, for
example pump and atomizer sprays, automatic fogging systems,
foggers, foams, gels, evaporator products with evaporator tablets
made of cellulose or polymer, liquid evaporators, gel and membrane
evaporators, propeller-driven evaporators, energy-free, or passive,
evaporation systems, moth papers, moth bags and moth gels, as
granules or dusts, in baits for spreading or in bait stations.
[0566] The active compounds according to the invention can also be
used as defoliants, desiccants, haulm killers and, in particular,
as weed killers. Weeds in the broadest sense are understood as
meaning all plants which grow at locations where they are
undesired. Whether the substances according to the invention act as
nonselective or selective herbicides depends essentially on the
application rate.
[0567] The active compounds according to the invention can be used,
for example, in the following plants:
[0568] Dicotyledonous weeds of the genera: Abutilon, Amaranthus,
Ambrosia, Anoda, Anthemis, Aphanes, Atriplex, Bellis, Bidens,
Capsella, Carduus, Cassia, Centaurea, Chenopodium, Cirsium,
Convolvulus, Datura, Desmodium, Emex, Erysimum, Euphorbia,
Galeopsis, Galinsoga, Galium, Hibiscus, Ipomoea, Kochia, Lamium,
Lepidium, Lindernia, Matricaria, Mentha, Mercurialis, Mullugo,
Myosotis, Papaver, Pharbitis, Plantago, Polygonum, Portulaca,
Ranunculus, Raphanus, Rorippa, Rotala, Rumex, Salsola, Senecio,
Sesbania, Sida, Sinapis, Solanum, Sonchus, Sphenoclea, Stellaria,
Taraxacum, Thlaspi, Trifolium, Urtica, Veronica, Viola,
Xanthium.
[0569] Dicotyledonous crops of the genera: Arachis, Beta, Brassica,
Cucumis, Cucurbita, Helianthus, Daucus, Glycine, Gossypium,
Ipomoea, Lactuca, Linum, Lycopersicon, Nicotiana, Phaseolus, Pisum,
Solanum, Vicia.
[0570] Monocotyledonous weeds of the genera: Aegilops, Agropyron,
Agrostis, Alopecurus, Apera, Avena, Brachiaria, Bromus, Cenchrus,
Commelina, Cynodon, Cyperus, Dactyloctenium, Digitaria,
Echinochloa, Eleocharis, Eleusine, Eragrostis, Eriochloa, Festuca,
Fimbristylis, Heteranthera, Imperata, Ischaemum, Leptochloa,
Lolium, Monochoria, Panicum, Paspalum, Phalaris, Phleum, Poa,
Rottboellia, Sagittaria, Scirpus, Setaria, Sorghum.
[0571] Monocotyledonous crops of the genera: Allium, Ananas,
Asparagus, Avena, Hordeum, Oryza, Panicum, Saccharum, Secale,
Sorghum, Triticale, Triticum, Zea.
[0572] However, the use of the active compounds according to the
invention is in no way restricted to these genera, but extends in
the same manner to other plants.
[0573] Depending on the concentration, the active compounds
according to the invention are suitable for the nonselective weed
control on, for example, industrial terrains and railway tracks and
on paths and locations with and without trees. Likewise the active
compounds according to the invention can be employed for
controlling weeds in perennial crops, for example forests,
ornamental tree plantings, orchards, vineyards, citrus groves, nut
orchards, banana plantations, coffee plantations, tea plantations,
rubber plantations, oil palm plantations, cocoa plantations, soft
fruit plantings and hop fields, on lawns, turf and pastureland, and
for the selective control of weeds in annual crops.
[0574] The compounds of the formula (I) according to the invention
have strong herbicidal activity and a broad activity spectrum when
used on the soil and on aerial plant parts. To a certain extent,
they are also suitable for the selective control of
monocotyledonous and dicotyledonous weeds in monocotyledonous and
dicotyledonous crops, both pre- and post-emergence.
[0575] At certain concentrations or application rates, the active
compounds according to the invention can also be employed for
controlling animal pests and fungal or bacterial plant diseases. If
appropriate, they can also be used as intermediates or precursors
for the synthesis of other active compounds. The active compounds
can be converted into the customary formulations, such as
solutions, emulsions, wettable powders, suspensions, powders,
dusting agents, pastes, soluble powders, granules, suspoemulsion
concentrates, natural and synthetic materials impregnated with
active compound, and very fine capsules in polymeric
substances.
[0576] 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.
[0577] If the extender used is water, it is also possible to use,
for example, organic solvents as auxiliary solvents. Suitable
liquid solvents are essentially: aromatics, such as xylene, toluene
or alkylnaphthalenes, chlorinated aromatics and chlorinated
aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or
methylene chloride, aliphatic hydrocarbons, such as cyclohexane or
paraffins, for example petroleum fractions, mineral and vegetable
oils, alcohols, such as butanol or glycol, and also their ethers
and esters, ketones, such as acetone, methyl ethyl ketone, methyl
isobutyl ketone or cyclohexanone, strongly polar solvents, such as
dimethylformamide and dimethyl sulfoxide, and also water.
[0578] Suitable solid carriers are: for example ammonium salts and
ground natural minerals, such as kaolins, clays, talc, chalk,
quartz, attapulgite, montmorillonite or diatomaceous earth, and
ground synthetic minerals, such as finely divided silica, alumina
and silicates, suitable solid carriers for granules are: for
example crushed and fractionated natural rocks such as calcite,
marble, pumice, sepiolite and dolomite, and also synthetic granules
of inorganic and organic meals, and granules of organic material
such as sawdust, coconut shells, maize cobs and tobacco stalks;
suitable emulsifiers and/or foam-formers are: for example non-ionic
and anionic emulsifiers, such as polyoxyethylene fatty acid esters,
polyoxyethylene fatty alcohol ethers, for example alkylaryl
polyglycol ethers, alkylsulfonates, alkyl sulfates, arylsulfonates
and protein hydrolysates; suitable dispersants are: for example
lignosulfite waste liquors and methylcellulose.
[0579] Tackifiers such as carboxymethylcellulose and natural and
synthetic polymers in the form of powders, granules or latices,
such as gum arabic, polyvinyl alcohol and polyvinyl acetate, and
also natural phospholipids, such as cephalins and lecithins, and
synthetic phospholipids, can be used in the formulations. Other
possible additives are mineral and vegetable oils.
[0580] It is possible to use colorants such as inorganic pigments,
for example iron oxide, titanium oxide and Prussian Blue, and
organic colorants, such as alizarin colorants, azo colorants and
metal phthalocyanine colorants, and trace nutrients such as salts
of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
[0581] The formulations generally comprise between 0.1 and 95
percent by weight of active compound, preferably between 0.5 and
90%.
[0582] The active compounds according to the invention, as such or
in their formulations, can also be used for weed control purposes
as a mixture with known herbicides and/or with substances which
improve crop plant tolerance ("safeners"), ready mixes or tank
mixes being possible. Mixtures with herbicide products which
contain one or more known herbicides and a safener are hence also
possible.
[0583] Herbicides which are suitable for the mixtures are known
herbicides, for example
acetochlor, acifluorfen (-sodium), aclonifen, alachlor, alloxydim
(-sodium), ametryne, amicarbazone, amidochlor, amidosulfuron,
aminopyralid, anilofos, asulam, atrazine, azafenidin, azimsulfuron,
beflubutamid, benazolin (-ethyl), bencarbazone, benfuresate,
bensulfuron (-methyl), bentazone, benzfendizone, benzobicyclon,
benzofenap, benzoylprop (-ethyl), bialaphos, bifenox, bispyribac
(-sodium), bromobutide, bromofenoxim, bromoxynil, butachlor,
butafenacil (-allyl), butroxydim, butylate, cafenstrole, caloxydim,
carbetamide, carfentrazone (-ethyl), chlomethoxyfen, chloramben,
chloridazon, chlorimuron (-ethyl), chlornitrofen, chlorsulfuron,
chlortoluron, cinidon (-ethyl), cinmethylin, cinosulfuron,
clefoxydim, clethodim, clodinafop (-propargyl), clomazone,
clomeprop, clopyralid, clopyrasulfuron (-methyl), cloransulam
(-methyl), cumyluron, cyanazine, cybutryne, cycloate,
cyclosulfamuron, cycloxydim, cyhalofop (-butyl), 2,4-D, 2,4-DB,
desmedipham, diallate, dicamba, dichlorprop (--P), diclofop
(-methyl), diclosulam, diethatyl (-ethyl), difenzoquat,
diflufenican, diflufenzopyr, dimefuron, dimepiperate, dimethachlor,
dimethametryn, dimethenamid, dimexyflam, dinitramine, diphenamid,
diquat, dithiopyr, diuron, dymron, epropodan, EPTC, esprocarb,
ethalfluralin, ethametsulfuron (-methyl), ethofumesate, ethoxyfen,
ethoxysulfuron, etobenzanid, fenoxaprop (--P-ethyl), fentrazamide,
flamprop (-isopropyl, -isopropyl-L, -methyl), flazasulfuron,
florasulam, fluazifop (--P-butyl), fluazolate, flucarbazone
(-sodium), flufenacet, flucetosulfuron, flumetsulam, flumiclorac
(-pentyl), flumioxazin, flumipropyn, flumetsulam, fluometuron,
fluorochloridone, fluoroglycofen (-ethyl), flupoxam, flupropacil,
flurpyrsulfuron (-methyl, -sodium), flurenol (-butyl), fluridone,
fluoroxypyr (-butoxypropyl, -meptyl), flurprimidol, flurtamone,
fluthiacet (-methyl), fluthiamide, fomesafen, foramsulfuron,
glufosinate (-ammonium), glyphosate (-isopropylammonium),
halosafen, haloxyfop (-ethoxyethyl, --P-methyl), hexazinone,
HOK-201, imazamethabenz (-methyl), imazamethapyr, imazamox,
imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron,
iodosulfuron (-methyl, -sodium), ioxynil, isopropalin, isoproturon,
isouron, isoxaben, isoxachlortole, isoxaflutole, isoxapyrifop,
lactofen, lenacil, linuron, MCPA, mecoprop, mefenacet,
mesosulfurone, mesotrione, metamifop, metamitron, metazachlor,
methabenzthiazuron, metobenzuron, metobromuron, (alpha-)
metolachlor, metosulam, metoxuron, metribuzin, metsulfuron
(-methyl), molinate, monolinuron, naproanilide, napropamide,
neburon, nicosulfuron, norflurazon, orbencarb, orthosulfamuron,
oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefone,
oxyfluorfen, paraquat, pelargonic acid, pendimethalin, pendralin,
penoxsulam, pentoxazone, phenmedipham, picolinafen, pinoxaden,
piperophos, pretilachlor, primisulfuron (-methyl), profluazol,
prometryn, propachlor, propanil, propaquizafop, propisochlor,
propoxycarbazone (-sodium), propyzamide, prosulfocarb, prosulfuron,
pyraflufen (-ethyl), pyrasulfotole, pyrazogyl, pyrazolate,
pyrazosulfuron (-ethyl), pyrazoxyfen, pyribenzoxim, pyributicarb,
pyridate, pyridatol, pyriftalide, pyriminobac (-methyl),
pyrithiobac (-sodium), pyrimisulfan, quinchlorac, quinmerac,
quinoclamine, quizalofop (--P-ethyl, --P-tefuryl), rimsulfuron,
sethoxydim, simazine, simetryn, sulcotrione, sulfentrazone,
sulfometuron (-methyl), sulfosate, sulfosulfuron, tebutam,
tebuthiuron, tembotrione, tepraloxydim, terbuthylazine, terbutryn,
thenylchlor, thiafluamide, thiazopyr, thidiazimin,
thiencarbazone-methyl, thifensulfuron (-methyl), thiobencarb,
tiocarbazil, topramezone, tralkoxydim, triallate, triasulfuron,
tribenuron (-methyl), triclopyr, tridiphane, trifluralin,
trifloxysulfuron, triflusulfuron (-methyl), tritosulfuron,
triflosulam,
##STR00088##
[0584] A mixture with other known active compounds, such as
fungicides, insecticides, acaricides, nematicides, bird repellents,
plant nutrients and soil conditioners, is also possible.
[0585] The active compounds or active compound combinations can be
applied as such, in the form of their formulations or the use forms
prepared therefrom by further dilution, such as ready-to-use
solutions, suspensions, emulsions, powders, pastes and granules.
They are applied in the customary manner, for example by pouring,
spraying, atomizing, spreading.
[0586] The active compounds or active compound combinations
according to the invention can be applied both before and after
plant emergence. They can also be incorporated into the soil prior
to planting.
[0587] The application rate of active compound can vary within a
substantial range. Essentially, it depends on the nature of the
desired effect. In general, the application rates are between 1 g
and 10 kg of active compound per hectare of soil area, preferably
between 5 g and 5 kg per ha.
[0588] The advantageous effect of the compatibility with crop
plants of the active compound combinations according to the
invention is particularly pronounced at certain concentration
ratios. However, the weight ratios of the active compounds in the
active compound combinations can be varied within relatively wide
ranges. In general,
salts from 0.001 to 1000 parts by weight, preferably from 0.01 to
100 parts by weight, particularly preferably 0.05 to 20 parts by
weight, of one of the compounds which improves crop plant
compatibility (antidotes/safeners) mentioned above under (b') are
present per part by weight of active compound of the formula
(I).
[0589] The active compound combinations according to the invention
are generally applied in the form of finished formulations.
However, the active compounds contained in the active compound
combinations can, as individual formulations, also be mixed during
use, i.e. be applied in the form of tank mixes.
[0590] For certain applications, in particular by the
post-emergence method, it may furthermore be advantageous to
include, as further additives in the formulations, mineral or
vegetable oils which are tolerated by plants (for example the
commercial preparation "Rako Binol"), or ammonium salts, such as,
for example, ammonium sulfate or ammonium thiocyanate.
[0591] The novel active compound combinations can be used as such,
in the form of their formulations or the use forms prepared
therefrom by further dilution, such as ready-to-use solutions,
suspensions, emulsions, powders, pastes and granules. Application
is in the customary manner, for example by pouring, spraying,
atomizing, dusting or scattering.
[0592] The application rates of the active compound combinations
according to the invention can be varied within a certain range;
they depend, inter alia, on the weather and on soil factors. In
general, the application rates are between 0.001 and 5 kg per ha,
preferably between 0.005 and 2 kg per ha, particularly preferably
between 0.01 and 0.5 kg per ha.
[0593] The active compound combinations according to the invention
can be applied before and after emergence of the plants, that is to
say by the pre-emergence and post-emergence method.
[0594] Depending on their properties, the safeners to be used
according to the invention can be used for pretreating the seed of
the crop plant (seed dressing) or can be introduced into the seed
furrows prior to sowing or be used separately prior to the
herbicide or together with the herbicide, before or after emergence
of the plants.
[0595] Examples of plants which may be mentioned are important crop
plants, such as cereals (wheat, barley, rice), maize, soybeans,
potatoes, cotton, oilseed rape, beet, sugar cane and also fruit
plants (with the fruits apples, pears, citrus fruits and
grapevines), greater emphasis being given to maize, soybeans,
potatoes, cotton and oilseed rape.
[0596] The term "active compounds" always also includes the active
compound combinations mentioned here.
[0597] Preparation and use of the active compounds according to the
invention is illustrated by the examples below.
Compounds of the Formula (I-a) Known from WO 01/74 770
TABLE-US-00010 (I-a) ##STR00089## Ex. No. D A B m.p. Isomer I-a-1 H
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2-- 244 .beta.
I-a-2 H --(CH.sub.2).sub.2--CHOC.sub.2H.sub.5--(CH.sub.2).sub.2--
212 .beta. I-a-3 H ##STR00090## CH.sub.3 227-229 -- I-a-4 H
C.sub.2H.sub.5 CH.sub.3 229-230 -- I-a-5 CH.sub.3 C.sub.2H.sub.5 H
220-224 -- I-a-6 ##STR00091## CH.sub.3 H 211-213 -- I-a-7
--(CH.sub.2).sub.3-- H 195-198 -- I-a-8
--CH.sub.2--CHOCH.sub.3--CH.sub.2-- H 233 -- I-a-9 ##STR00092## H
*4.29 (dd, 1 H, C.sub.5--H)--6.84 (s, 2 H, Ar--H) -- I-a-10 H
--(CH.sub.2).sub.2--CHCH.sub.3--(CH.sub.2).sub.2-- *0.91 (d, 3 H,
CH.sub.3-.beta.) .beta. Spiral cycle 6.84 (s, 2 H, Ar--H) I-a-11 H
--(CH.sub.2).sub.2--CHCF.sub.3--(CH.sub.2).sub.2-- Oil .beta. log P
3.05 *.sup.1H-NMR (400 MHz, d.sub.6-DMSO): shifts .delta. in
ppm
PREPARATION EXAMPLES
Example I-b-1
##STR00093##
[0599] Under reflux, 0.052 g (0.48 mmol) of methoxyacetal chloride
in 2 ml of ethyl acetate is added to 0.15 g (0.437 mmol) of the
compound of preparation example I-a-1 and 0.049 g (0.48 mmol) of
triethylamine and 10 ml of ethyl acetate. The mixture is stirred
under reflux for 20 h, and the reaction is monitored by thin-layer
chromatography. After the reaction has ended, 2 ml of saturated
NaHO.sub.3 solution are added, and the mixture is stirred at room
temperature for 10 min.
[0600] The organic phase is separated off, the solvent is removed
using a rotary evaporator and the precipitate is saturated with
n-heptane. The precipitate is filtered off with suction.
[0601] Yield: 0.137 g (76% of theory)
[0602] .sup.1H-NMR (300 MHz, CDCl.sub.3): .delta.=6.89 (s, 2H,
Ar--H), 3.96 (s, 2H, CH.sub.2OCH.sub.3), 3.22 (m, 1H,
CH--OCH.sub.3) ppm.
[0603] Analogously to example (I-b-1) and in accordance with the
general statements on the preparation, the following compounds of
the formula (I-b) are obtained
TABLE-US-00011 (I-b) ##STR00094## Ex. No. D A B R.sup.1 m.p.
.degree. C. Isomer I-b-2 H
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2--
H.sub.5C.sub.2--O--CH.sub.2-- 138-141 .beta. I-b-3 H
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2--
i-C.sub.3H.sub.7 182-185 .beta. I-b-4 H ##STR00095## CH.sub.3
i-C.sub.3H.sub.7 128-129 -- I-b-5 H C.sub.2H.sub.5 CH.sub.3
i-C.sub.3H.sub.7 120 -- I-b-6 H CH.sub.3 CH.sub.3 i-C.sub.3H.sub.7
166-168 -- I-b-7 H ##STR00096## CH.sub.3
H.sub.5C.sub.2--O--CH.sub.2-- 115 -- 1-b-8 H CH.sub.3 CH.sub.3
H.sub.3C--O--CH.sub.2-- *3.97 (s, 2 H, CH.sub.2--O) 6.89 (s, 2 H,
Ar--H) I-b-9 H --(CH.sub.2).sub.2--CHCH.sub.3--(CH.sub.2).sub.2--
H.sub.3C--O--CH.sub.2-- *3.94 (s, 2 H, CH.sub.2--O) .beta. 6.89 (s,
2 H, Ar--H) I-b-10 --CH.sub.2--CHOCH.sub.3--CH.sub.2-- H
i-C.sub.3H.sub.7 *3.37 (s, 3 H, O--CH.sub.3) -- 6.89 (s, 2 H,
Ar--H) I-b-11 CH.sub.3 C.sub.2H.sub.5 H i-C.sub.3H.sub.7 *3.03 (s,
3 H, N--CH.sub.3) -- 6.89 (s, 2 H, Ar--H) I-b-12 ##STR00097##
CH.sub.3 H i-C.sub.3H.sub.7 *0.76 (m, 2 H,
CH.sub.2-cyclopropyl),6.88 (d, 2 H, Ar--H) -- I-b-13
--(CH.sub.2).sub.3-- H i-C.sub.3H.sub.7 *4.71 (dd, 1 H, C5--H) --
6.89 (d, 2 H, Ar--H) I-b-14 ##STR00098## H i-C.sub.3H.sub.7 *2.58
(m, 1 H,CH(CH.sub.3).sub.2--4.97 (dd, 1 H, C5--H)6.92 (s, 2 H,
Ar--H) -- I-b-15 H
--(CH.sub.2).sub.2--CHCH.sub.3--(CH.sub.2).sub.2-- i-C.sub.3H.sub.7
*.sup.1)0.96 (d, 6 H, .beta. CH(CH.sub.3).sub.2) 2.29 (s, 3 H,
Ar--CH.sub.3) *.sup.1H-NMR (300 MHz, CDCl.sub.3): shifts .delta. in
ppm *.sup.1)measured in CD.sub.3OD
Example I-c-1
##STR00099##
[0605] 0.21 g (0.6 mmol) of the compound of preparation example
(I-a-1) was suspended in 10 ml of dichloromethane, and 0.1 ml of
triethylamine and 0.08 g (0.66 mmol) of allyl chloroformate were
then added at room temperature. The mixture was stirred over the
weekend, and 10 ml of 5% strength sodium carbonate solution was
added. After 4 h of stirring, the organic phase was separated off
and concentrated to dryness. The residue obtained in this manner
was taken up in 1 ml of ethyl acetate, and 2 ml of n-heptane were
added. The solid is filtered off with suction.
[0606] Yield: 84 mg (32.7% of theory) m.p.: 155-157.degree. C.
[0607] Analogously to example (I-c-1) and in accordance with the
general statements on the preparation, the following compounds of
the formula (I-c) are obtained
TABLE-US-00012 (I-c) ##STR00100## Ex. No. D A B M R.sup.2 m.p.
.degree. C. Isomer I-c-2 H
--(CH.sub.2).sub.2--CHOCH.sub.3--(CH.sub.2).sub.2-- O
C.sub.2H.sub.5 149 .beta. I-c-3 H CH.sub.3 CH.sub.3 O
C.sub.2H.sub.5 182-184 -- I-c-4 CH.sub.3 C.sub.2H.sub.5 H O
C.sub.2H.sub.5 *3.03 (s, 3 H, NCH.sub.3) -- 4.18 (m, 2 H,
CH.sub.2--O) 6.92 (s, 2 H, Ar--H) I-c-5 C.sub.2H.sub.5 CH.sub.3 H O
C.sub.2H.sub.5 *1.47 (d, 3 H, CHCH.sub.3) -- 4.18 (m, 2 H,
CH.sub.2--O) 6.91 (s, 2 H, Ar--H) I-c-6 --(CH.sub.2).sub.3-- H O
C.sub.2H.sub.5 *4.18 (m, 2 H, CH.sub.2--O) -- 4.74 (dd, 1 H, C5--H)
6.92 (d, 2 H, Ar--H) I-c-7 --CH.sub.2--CHOCH.sub.3--CH.sub.2-- H O
C.sub.2H.sub.5 *3.36 (s, 3 H, OCH.sub.3) -- 4.18 (m, 2 H,
CH.sub.2--O) 6.92 (d, 2 H, Ar--H) *.sup.1H-NMR (300 MHz,
CDCl.sub.3): shifts .delta. in ppm
Example I-e-1
##STR00101##
[0609] 0.15 g (0.5 mmol) of the compound of example I-a-3 is
initially charged in acetonitrile (10 ml), and 0.083 g of potassium
carbonate (1.2 eq) is added. After 30 min, dibutylphosphoryl
chloride (0.126 g, 1.1 eq) is added, and the mixture is stirred at
TR for 48 h. The solid is filtered with suction and the organic
solution is concentrated and purified by chromatography
(n-heptane/ethyl acetate 9:1 to 1:4). This gives 82 mg of a
colorless oil (yield 32% of theory).
[0610] .sup.1H-NMR (300 MHz, CDCl.sub.3): .delta.=0.21 (m, 2H,
CH.sub.2 from CycPr), [0611] 6.92 (d, 2H, Ar--H)
[0612] The compounds of the formula (I-a) can be prepared by the
processes described in WO 01/74770:
##STR00102##
[0613] Here, the substituents A, B and D are as defined above and
Alk represents C.sub.1-C.sub.8-alkyl, preferably methyl or
ethyl.
[0614] Analogously to G. C. Lloyd-Jones, Angew. Chem. Int. Ed.
2002, 41, 953-956; S. L. Buchwald, W. A. Moradi, JACS 2001, 123,
7996-8002 and S. Lee, N. A. Beare, J. F. Hartwig JACS 2001, 123,
8410-8411, an improved process for preparing
2,6-diethyl-4-methylphenyl acetic acid was found.
[0615] The process is characterized in that
2,6-diethyl-4-methylbromobenzene is reacted with tert-butyl
acetate, if appropriate in the presence of a diluent, if
appropriate in the presence of a base, if appropriate in the
presence of a phosphine ligand and if appropriate in the presence
of palladium (0) compounds, and then reacted with an acid.
[0616] Suitable diluents for use in the process according to the
invention are all solvents which are inert to the reagents.
Preference is given to using hydrocarbons, such as benzine,
benzene, toluene, xylene and tetraline, furthermore ethers, such as
diethyl ether, dimethoxyethane, tetrahydrofuran and dioxane.
[0617] Suitable bases for the reaction according to the process
according to the invention are lithium amide bases, preferably
lithium hexyldisilazide, lithium diisopropylamide, lithium
dicyclohexylamide.
[0618] Suitable phosphine ligands are, for example, in particular
tri-tert-butylphosphine and
2-dicyclohexylphosphino(2'-N,N-dimethylamino)biphenyl.
[0619] A palladium (0) compound which may be mentioned by way of
example is bis-(dibenzylideneacetone)-palladium.
[0620] Acids which may be mentioned are organic acids, for example
formic acid, or inorganic acids, for example hydrochloric acid or
sulfuric acid.
[0621] The reaction temperature in the process according to the
invention may be varied within a relatively wide range. In general,
the process is carried out at temperatures between -80.degree. C.
and +150.degree. C., preferably between 0.degree. C. and
100.degree. C.
[0622] When carrying out the process according to the invention,
the starting materials are generally each employed in approximately
equivalent amounts.
[0623] A further process for preparing
2,6-diethyl-4-methylphenylacetic acid comprises the reaction of
2,6-diethyl-4-methylphenylmalodinitrile with acids, if appropriate
in the presence of a diluent, and the subsequent reaction with an
acid.
[0624] Suitable acids are mineral acids, for example concentrated
sulfuric acid.
[0625] The reaction temperature may be varied within a relatively
wide range. In general, the process is carried out at temperatures
between 0 and 150.degree. C. The starting materials are generally
each employed in approximately equivalent amounts.
[0626] By reacting 2,6-diethyl-4-methylphenylacetic acid with
halogenating agents, if appropriate in the presence of a diluent,
2,6-diethyl-4-methylphenylacetyl chloride is obtained (WO
01/74770).
Component D'
Route 1
##STR00103##
[0628] 3.6 g (7.5 mmol) of component B' and 30 ml of
dichloromethane are added dropwise to 2.32 ml of sulfuric acid. The
mixture is stirred at 35.degree. C. for 2 hours, and 3.25 ml of
methanol are added. The mixture is stirred at 60.degree. C. for 6
hours and left at room temperature overnight. The reaction mixture
is poured into water and extracted with dichloromethane. The
solvent is distilled off and the residue is taken up in ethyl
acetate/n-heptane 1:4. The residue is filtered off with suction
through a frit, washed with ethyl acetate/n-heptane 1:4, dried (0.5
g), and the solvent is removed using a rotary evaporator. The
residue of the mother liquor is purified by column-chromatographic
separation (silica gel, ethyl acetate/n-heptane 1:4.fwdarw.1:1. The
fractions are concentrated using a concentrated evaporator, stirred
with ethyl acetate/n-heptane 1:9 for 10 minutes and filtered off
with suction through a frit, and the filter cake is washed with
n-heptane and dried (0.85 g).
[0629] Total yield: 1.35 g (52% of theory), m.p. 95.degree. C.
Component B'
##STR00104##
[0631] 1.3 g of 2-amino-2-cyclopropylpropionitrile and 1.64 ml of
triethylamine are initially charged in 50 ml of tetrahydrofuran.
With ice-cooling, 2.66 g of 2,6-diethyl-4-methylphenylacetyl
chloride in 50 ml of tetrahydrofuran are added, and the mixture is
stirred for 3 days with monitoring by thin-layer chromatography.
The triethylamine hydrochloride is filtered off with suction, the
solvent is removed under reduced pressure and the residue is used
without further purification for preparing the components D' (route
1).
[0632] Yield: 3.65 g (58 of theory)
Component D'
Route 2
##STR00105##
[0634] At 20.degree. C., 12 g (100.1 mmol) of thionyl chloride are
added to 4.13 g (20 mmol) of 2,6-diethyl-4-methylphenylacetic acid
in 20 ml of toluene. The mixture is stirred under reflux for 2 h
and the solvent is distilled off. The residue is dissolved in 20 ml
of tetrahydrofuran and, at 0 to 5.degree. C., added dropwise to a
suspension of 4.48 g of methyl
1-amino-4-methoxycyclohexanecarboxylic hydrochloride (0.020 mol)
and 6.1 ml (44 mmol) of triethylamine and 100 ml of
tetrahydrofuran.
[0635] The mixture is stirred at 40.degree. C. for 1 h (monitored
by TLC). The solvent is removed using a rotary evaporator. The
residue is purified by column chromatography on silica gel
(hexane:ethyl acetate, 2:1).
[0636] Yield: 5.9 g (72% of theory), m.p. 113.degree. C.
Example I-a-1
##STR00106##
[0638] At 60.degree. C., 5.7 g of component D' (route 2) in 15 ml
of dimethylactamide are added to 3.9 g of potassium tert-butoxide
in 20 ml of dimethylacetamide. The mixture is stirred at 80.degree.
C. and the reaction is monitored by TLC. The reaction solution is
added to 200 ml of ice-water, the pH is adjusted to 2 using
concentrated hydrochloric acid and the precipitate is filtered off
with suction. The precipitate is purified using methyl tert-butyl
ether/hexane.
[0639] The product is purified by column chromatography on silica
gel (dichloromethane; ethyl acetate, 3:1).
[0640] Yield: 5 g (97% of theory)
Preparation of 2,6-diethyl 4-methylphenyl acetic acid
Component K
##STR00107##
[0642] At 15.degree. C., 5.6 g of tert-butyl acetate were added to
57.2 mmol of a freshly prepared lithium dicyclohexylamide solution.
During the addition, the temperature increased from 15.degree. C.
to 25.degree. C. After 10 min, a degassed mixture of 10 g of
2,6-diethyl-4-methylbromobenzene and 0.253 g of
bis(dibenzylideneacetone)palladium and 0.089 g of
tri-tert-butylphosphine as a 0.5 molar solution in toluene was
added. Over a period of 30 min, the temperature increased to
35.degree. C., and over a period of half an hour, the temperature
then cooled to 28.degree. C. The reaction mixture was put into a
mixture of 10 ml of hydrochloric acid and 200 ml of water, and 400
ml of dichloromethane were added. After 30 min of stirring, the
solid was separated off and washed with dichloromethane. The
organic phase was removed from the mother liquor and dried with
magnesium sulfate. Column filtration on silica gel using ethyl
acetate/n-heptane 1:6 gave 12.1 g of product. The viscous oil was
reacted further without further purification.
##STR00108##
[0643] At room temperature, 12 g of component K were stirred in 100
ml of formic acid for 2 h. The mixture was then poured into 400 ml
of ice-water and stirred for 30 min, and the solid formed was
filtered with suction. For drying, the residue was taken up in
dichloromethane and this solution was dried with magnesium sulfate.
After concentration, the residue was digested in a little n-heptane
and filtered off with suction. This gave 8.2 g of
2,6-diethyl-4-methylphenylacetic acid, which corresponds to a total
yield of 90% over all steps. M.p. 124.degree. C.
2,6-Diethyl-4-methylphenylacetic acid
[0644] Under an atmosphere of argon, 20.0 g of
2,6-diethyl-4-methylphenylmalodinitrile (94.2 mmol), known from WO
00/78712, are heated in a mixture of 128 g of concentrated sulfuric
acid and 48 ml of water at 140.degree. C. for 24 h. After cooling,
the mixture is repeatedly extracted with dichloromethane and the
extracts are washed twice with water, dried (sodium sulfate) and
concentrated. This gives 18.8 g of colorless crystals of melting
point 116 to 117.degree. C.
[0645] .sup.1H-NMR (CDCl.sub.3, 300 MHz): .delta.=1.19 (t, 6H),
2.28 (s, 3H), 2.60 (q, 4H), 3.73 (s, 2H), 6.90 (s, 2H)
Methyl 2,6-diethyl-4-methylphenylacetate
[0646] 1 ml of concentrated sulfuric acid is added to 18.0 g (87.3
mmol) of 2,6-diethyl-4-methylphenylacetic acid and 300 ml of
absolute methanol, and the mixture is heated at reflux for 4 h.
After cooling, the mixture is extracted with ethyl acetate, the
extracts are washed with water in sodium carbonate solution and
dried (magnesium sulfate) and the solvent is distilled off. This
gives 18.37 g of (95%) of the desired product as a colorless
oil.
[0647] .sup.1H-NMR (CDCl.sub.3, 300 MHz): .delta.=1.20 (t, 6H),
2.32 (s, 3H), 2.62 (1, 4H), 3.67 (s, 3H), 2.72 (s, 2H), 6.93 (s,
2H)
Use Examples
Example A
1. Herbicidal Pre-Emergence Action
[0648] Seeds of monocotyledonous and dicotyledonous weed and crop
plants are placed in sandy loam in wood fiber pots and covered with
soil. The test compounds, formulated in the form of wettable
powders (WP), are then, as an aqueous suspension with a water
application rate of 600 l/ha (converted), with 0.2% of wetting
agent added, applied to the surface of the covering soil in various
dosages.
[0649] After the treatment, the pots are placed in a greenhouse and
kept under good growth conditions for the test plants. The visual
assessment of the emergence damage on the test plants is carried
out after a trial period of 3 weeks by comparison with untreated
controls (herbicidal effect in percent (%): 100% effect=the plants
have died, 0% effect=like control plants).
[0650] In addition to the examples explicitly mentioned, the
following compounds, at an application rate of 320 g/ha, show an
activity of .gtoreq.80% against Avena sativa, Lolium multiflorum
and Setaria viridis: I-a-8, I-a-9, I-b-5, I-b-13, I-b-14,
I-c-3.
2. Herbicidal Post-Emergence Action
[0651] Seeds of monocotyledonous and dicotyledonous weed and crop
plants are placed into sandy loam in wood fiber pots, covered with
soil and cultivated in a greenhouse under good growth conditions.
Two-three weeks after sowing, the test plants are treated at the
one-leaf stage. The test compounds, formulated as wettable powders
(WP), are then, in various dosages with a water application rate of
600 l/ha (converted), with 0.2% of wetting agent added, sprayed
onto the green parts of the plants. After the test plants have been
kept in the greenhouse under optimum growth conditions for about 3
weeks, the effect of the preparations is rated visually in
comparison to untreated controls (herbicidal effect in percent (%):
100% effect=the plants have died, 0% effect=like control
plants).
[0652] In addition to the examples explicitly mentioned, the
following compounds, at an application rate of 320 g/ha, show an
activity of .gtoreq.80% against Avena sativa, Echinochloa
crus-galli, Lolium multiflorum and Setaria viridis: I-a-2, I-a-4,
I-a-8, I-a-10, I-b-3, I-b-4, I-b-5, I-b-6, I-b-7, I-b-8, I-b-11,
I-b-13, I-b-14, I-c-3, I-c-4, I-c-5, I-c-6.
TABLE-US-00013 g of Greenhouse a.i./ha Alopecurus Avena fatua
Lolium Setaria Veronica Ex. No. I-b-1 post-emergence 80 100 100 100
100 80 g of Greenhouse a.i./ha Alopecurus Echinochloa Lolium
Setaria Veronica Ex. No. I-c-2 pre-emergence 80 90 100 100 90 --
post-emergence 80 100 100 100 100 80 g of Greenhouse a.i./ha
Alopecurus Avena fatua Echinochloa Lolium Setaria Ex. No. I-c-1
pre-emergence 80 100 60 100 100 100 post-emergence 80 100 90 100
100 100 g of Greenhouse a.i./ha Alopecurus Avena fatua Lolium
Setaria Veronica Ex. No. I-b-2 pre-emergence 320 100 90 100 100 100
post-emergence 80 100 100 100 100 70
Example B
2. Herbicidal Post-Emergence Action
[0653] Seeds of monocotyledonous and dicotyledonous weed and crop
plants are placed into sandy loam in wood fiber pots or in plastic
pots, covered with soil and cultivated in a greenhouse, during the
vegetation period also outdoors outside of the greenhouse, under
good growth conditions. Two-three weeks after sowing, the test
plants are treated at the one- to three-leaf stage. The test
compounds, formulated as wettable powders (WP) or liquid (EC) are,
in various dosages with a water application rate of 300 l/ha
(converted), with wetting agent (0.2 to 0.3%) added, sprayed onto
the plants and the surface of the soil. Three-four weeks after the
treatment of the test plants, the effect of the preparations is
rated visually in comparison to untreated controls (herbicidal
effect in percent (%): 100% effect=the plants have died, 0%
effect=like control plants).
Use of Safeners
[0654] If it is additionally to be tested as to whether safeners
can improve the plant compatibility of test substances in the case
of crop plants, the following options are used for applying the
safener: [0655] seeds of the crop plants are, before sowing,
dressed with the safener substance (the amount of safener stated in
percent, based on the weight of the seed) [0656] before the
application of the test substances, the crop plants are sprayed
with the safener at a certain application rate per hectare (usually
1 day before the application of the test substances) [0657] the
safener is applied together with the test substance as a tank mix
(the amount of safener is stated in g/ha or as a ratio, based on
the herbicide).
[0658] By comparing the effect of the test substances on crop
plants without or with safener treatment, it is possible to assess
the effect of the safener substance.
Container Trials with Cereal in a Greenhouse
Post-Emergence Treatment
TABLE-US-00014 [0659] Application Summer barley g of a.i./ha
observed (%) Example 50 93 I-a-1 25 60 12.5 20 Example 50 + 100 60
I-a-1 + 25 + 100 20 mefenpyr 12.5 + 100 10 Example 25 60 I-c-1 12.5
35 Example 25 + 100 40 I-c-1 + 12.5 + 100 25 mefenpyr
Mefenpyr 1 day prior to herbicide application
TABLE-US-00015 28 days after application Application Summer wheat g
of a.i./ha observed (%) Example 25 90 I-b-1 Example 25 + 100 50
I-b-1 + mefenpyr 28 days after application Application Summer
barley Summer wheat g of a.i./ha observed (%) observed (%) Example
50 50 I-a-2 25 25 80 12.5 40 Example 50 + 100 20 I-a-2 + 25 + 100
10 40 mefenpyr 12.5 + 100 0 28 days after application Application
Summer wheat g of a.i./ha observed (%) Example 12.5 95 I-b-2
Example 12.5 + 100 30 I-b-2 + mefenpyr
Example C
TABLE-US-00016 [0660] Myzus test - (spray treatment) Solvents: 78
parts by weight of acetone 1.5 parts by weight of dimethylformamide
Emulsifier: 0.5 part by weight of alkylaryl polyglycol ether
[0661] To produce a suitable preparation of active compound, 1 part
by weight of active compound is mixed with the stated amounts of
solvents and emulsifier, and the concentrate is diluted with
emulsifier-containing water to the desired concentration.
[0662] Disks of Chinese cabbage (Brassica pekinensis) which are
infested by all stages of the green peach aphid (Myzus persicae)
are sprayed with a preparation of active compound of the desired
concentration.
[0663] After the desired period of time, the activity in % is
determined. 100% means that all aphids have been killed, 0% means
that none of the aphids have been killed.
[0664] In this test, for example, the following compounds of the
preparation examples, at 500 g/ha of a.i., show an activity of
.gtoreq.90% after 5 d: I-a-2, I-a-10, I-a-11, I-b-1, I-b-2.
Example D
TABLE-US-00017 [0665] Tetranychus test - (OP-resistance/spray
treatment) Solvents: 78 parts by weight of acetone 1.5 parts by
weight of dimethylformamide Emulsifier: 0.5 part by weight of
alkylaryl polyglycol ether
[0666] To produce a suitable preparation of active compound, 1 part
by weight of active compound is mixed with the stated amounts of
solvents and emulsifier, and the concentrate is diluted with
emulsifier-containing water to the desired concentration.
[0667] Disks of bean leaves (Phaseolus vulgaris) infested by all
stages of the greenhouse red spider mite (Tetranychus urticae) are
sprayed with a preparation of active compound of the desired
concentration.
[0668] After the desired period of time, the activity in % is
determined. 100% means that all spider mites have been killed, 0%
means that none of the spider mites have been killed.
[0669] In this test, for example, the following compounds of the
preparation examples, at application rates of 100 g/ha of a.i.,
show an activity of .gtoreq.70% after 5 d: I-a-4, I-b-1, I-b-2,
I-c-3, I-c-4, I-c-7.
Example E
TABLE-US-00018 [0670] Meloidogyne test - (spray treatment) Solvent:
80 parts by weight of acetone
[0671] To produce a suitable preparation of active compound, 1 part
by weight of active compound is mixed with the stated amounts of
solvent, and the concentrate is diluted with water to the desired
concentration.
[0672] Vessels are filled with sand, solution of active compound,
Meloidogyne incognita egg/larva suspension and lettuce seeds. The
lettuce seeds germinate and the plants develop. On the roots, galls
are formed.
[0673] After the desired period of time, the nematicidal activity
is determined in % by the formation of galls. 100% means that no
galls have been found; 0% means that the number of galls on the
treated plants corresponds to that of the untreated control.
[0674] In this test, for example, the following compounds of the
preparation examples, at an application rate of 20 ppm of a.i.,
show an activity of .gtoreq.70% after 14 d: I-b-2.
Example F
TABLE-US-00019 [0675] Phaedon test (PHAECO spray treatment)
Solvents: 78 parts by weight of acetone 1.5 parts by weight of
dimethylformamide Emulsifier: 0.5 part by weight of alkylaryl
polyglycol ether
[0676] To produce a suitable preparation of active compound, 1 part
by weight of active compound is mixed with the stated amounts of
solvents and emulsifier, and the concentrate is diluted with
emulsifier-containing water to the desired concentration.
[0677] Disks of Chinese cabbage (Brassica pekinensis) are sprayed
with a preparation of active compound of the desired concentration
and, after drying, populated with larvae of the mustard beetle
(Phaedon cochleariae).
[0678] After the desired period of time, the effect in % is
determined. 100% means that all beetle larvae have been killed; =%
means that none of the beetle larvae have been killed.
[0679] In this test, for example, the following compounds of the
preparation examples, at application rates of 500 g/ha of a.i.,
show an activity of .gtoreq.80% after 7 d: I-a-2, I-a-11, I-b-1,
I-b-2.
Example G
TABLE-US-00020 [0680] Critical concentration test/soil insects -
treatment of transgenic plants Test insect: Diabrotica balteata -
larvae in the soil Solvent: 7 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
[0681] To produce a suitable preparation of active compound, 1 part
by weight of active compound is mixed with the stated amount of
solvent, the stated amount of emulsifier is added and the
concentrate is diluted with water to the desired concentration.
[0682] The preparation of active compound is poured onto the soil.
Here, the concentration of active compound in the preparation is
virtually immaterial; only the amount by weight of active compound
per volume unit of soil, which is stated in ppm (mg/l) matters. The
soil is filled into 0.25 l pots, and these are allowed to stand at
20.degree. C.
[0683] Immediately after the preparation, 5 pregerminated maize
corns of the cultivar YIELD GUARD (trademark of Monsanto Comp.,
USA) are placed into each pot. After 2 days, the appropriate test
insects are placed into the treated soil. After a further 7 days,
the efficacy of the active compound is determined by counting the
maize plants that have emerged (1 plant=20% activity).
Example H
TABLE-US-00021 [0684] Heliothis virescens test - treatment of
transgenic plants Solvent: 7 parts by weight of acetone Emulsifier:
1 part by weight of alkylaryl polyglycol ether
[0685] 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.
[0686] Soybean shoots (Glycine max) of the cultivar Roundup Ready
(trademark of Monsanto Comp. USA) are treated by being dipped into
the preparation of active compound of the desired concentration and
are populated with the tobacco butterworm Heliothis virescens while
the leaves are still moist.
[0687] After the desired period of time, the kill of the insects is
determined.
* * * * *