U.S. patent application number 10/206426 was filed with the patent office on 2003-07-10 for phenyl-substituted cyclic enaminones.
Invention is credited to Dollinger, Markus, Drewes, Mark Wilhelm, Erdelen, Christoph, Feucht, Dieter, Fischer, Reiner, Philipp, Ulrich, Rauch, Olga-Tatjana, Wachendorff-Neumann, Ulrike, Wetcholowsky, Ingo, Wischnat, Ralf.
Application Number | 20030130125 10/206426 |
Document ID | / |
Family ID | 7887420 |
Filed Date | 2003-07-10 |
United States Patent
Application |
20030130125 |
Kind Code |
A1 |
Fischer, Reiner ; et
al. |
July 10, 2003 |
Phenyl-substituted cyclic enaminones
Abstract
The present invention relates to novel phenyl-substituted cyclic
enaminones of the formula (I): 1 in which Ar, X, Z, Y, K, n and m
are each as defined in the description, to a plurality of processes
and intermediates for their preparation and to their use as
herbicides and pesticides.
Inventors: |
Fischer, Reiner; (Monheim,
DE) ; Wischnat, Ralf; (Koln, DE) ; Drewes,
Mark Wilhelm; (Langenfeld, DE) ; Dollinger,
Markus; (Leverkusen, DE) ; Erdelen, Christoph;
(Leichlingen, DE) ; Feucht, Dieter; (Monheim,
DE) ; Wetcholowsky, Ingo; (Cond. Estancia Marambaia,
BR) ; Wachendorff-Neumann, Ulrike; (Neuwied, DE)
; Philipp, Ulrich; (Koln, DE) ; Rauch,
Olga-Tatjana; (Kronberg, DE) |
Correspondence
Address: |
BAYER CORPORATION
PATENT DEPARTMENT
100 BAYER ROAD
PITTSBURGH
PA
15205
US
|
Family ID: |
7887420 |
Appl. No.: |
10/206426 |
Filed: |
July 26, 2002 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10206426 |
Jul 26, 2002 |
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09831261 |
Jul 16, 2001 |
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6455472 |
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09831261 |
Jul 16, 2001 |
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PCT/EP99/08366 |
Nov 2, 1999 |
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Current U.S.
Class: |
504/283 ;
548/517; 548/571 |
Current CPC
Class: |
C07D 207/20 20130101;
C07C 323/62 20130101; C07D 409/06 20130101; C07D 215/14 20130101;
C07D 405/06 20130101; C07D 403/06 20130101; C07D 401/06 20130101;
C07C 255/40 20130101; C07D 223/04 20130101; C07D 417/14 20130101;
E04B 1/043 20130101; C07D 417/06 20130101; C07C 317/44 20130101;
C07D 401/10 20130101; C07D 211/70 20130101; C07D 207/22
20130101 |
Class at
Publication: |
504/283 ;
548/517; 548/571 |
International
Class: |
A01N 043/36; C07D
207/04; C07D 207/46; C07D 43/02 |
Foreign Application Data
Date |
Code |
Application Number |
Nov 2, 1998 |
DE |
198 51 986.9 |
Claims
1. Compounds of the general formula (I) 108in which K represents
oxygen or sulphur, Ar represents in each case substituted phenyl,
naphthyl or represents in each case optionally substituted mono- or
bicyclic hetaryl having 5 to 10 ring atoms, X represents CN, 109Y
represents halogen or in each case optionally substituted alkyl,
alkoxy, phenyl, phenylalkyl, hetaryl, hetarylalkyl or represents
the groups 110 two adjacent Y.sub.n represent an in each case
optionally substituted saturated or unsaturated cycle which may
optionally be interrupted by heteroatoms, and Z represents
hydrogen, represents in each case optionally substituted alkyl,
alkenyl, alkinyl, cycloalkyl, cycloalkyl-alkyl, alkoxyalkyl,
phenoxyalkyl, phenylalkyl-oxyalkyl, phenylthioalkyl,
phenylalkyl-thioalkyl, phenyl, phenylalkyl, hetaryl, hetaryl-alkyl
or represents the groups 111 or cyano, l represents 0 to 3, m
represents 1 to 3, n represents, depending on m, 0 to 4, R.sup.1
represents hydrogen, represents in each case optionally
substituted, saturated or unsaturated alkyl or cycloalkyl, each of
which is optionally interrupted by heteroatoms, represents in each
case optionally substituted phenyl or hetaryl, represents in each
case optionally substituted phenylalkyl or hetarylalkyl, R.sup.2
represents hydrogen, represents in each case optionally
substituted, saturated or unsaturated alkyl or alkoxy, represents
in each case optionally substituted phenyl, phenylalkyl or
phenylalkyloxy, or R.sup.1, R.sup.2 together with the nitrogen atom
to which they are attached represents an optionally substituted
cycle which is optionally interrupted by heteroatoms, R.sup.3
represents hydrogen, represents in each case optionally substituted
alkyl or alkoxy, represents in each case optionally substituted
phenyl or phenylalkyl, R.sup.4 represents hydrogen or represents
optionally substituted alkyl, and R.sup.5,R.sup.6 independently of
one another represent hydrogen or represent optionally substituted
alkyl, except for compounds of the following formula 112
2. Compounds according to claim 1, characterized in that Ar
represents Ar.sup.1, where Ar.sup.1 represents phenyl, naphthyl or
mono- or bicyclic hetaryl having five to ten ring atoms, each of
which radicals is optionally mono- to pentasubstituted by halogen,
C.sub.1-C.sub.8-alkyl, C.sub.2-C.sub.8-alkenyl,
C.sub.2-C.sub.8-alkinyl, C.sub.1-C.sub.8-alkoxy,
C.sub.2-C.sub.8-alkenyloxy, C.sub.3-C.sub.8-alkinyloxy,
C.sub.1-C.sub.8-alkylthio, C.sub.1-C.sub.6-alkylsulfinyl,
C.sub.1-C.sub.6-alkylsulfonyl, C.sub.1-C.sub.6-halogenoalkyl,
C.sub.1-C.sub.6-halogeno-alkoxy,
C.sub.2-C.sub.8-halogeno-alkenyloxy,
C.sub.1-C.sub.2-alkylidenediyl-dioxy,
C.sub.1-C.sub.2-halogenoalkylidened- iyl-dioxy,
halogeno-C.sub.1-C.sub.4-alkylthio, halogeno-C.sub.1-C.sub.4-al-
kylsulfinyl, halogeno-C.sub.1-C.sub.4-alkylsulfonyl, hydroxyl,
mercapto, nitro, cyano, amino, or by the groups a) -L-CO--R.sup.7,
113 or represents Ar.sup.2, where Ar.sup.2 represents Ar.sup.1
which is additionally substituted by phenyl, naphthyl, five- or
six-membered hetaryl, phenyl-C.sub.1-C.sub.4-alkyl, phenoxy,
phenyl-S(O).sub.g--, five- or six-membered hetaryloxy or
hetaryl-S(O).sub.g, where these substituents for their part are in
each case optionally mono- to tetrasubstituted by halogen,
C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.4-halogenoalkyl, C.sub.1-C.sub.4-halogenoalkoxy,
nitro or cyano, and K represents oxygen or sulphur, L represents
oxygen or sulphur, X represents CN, 114Y represents halogen,
--C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.4-halogenoalky- l,
C.sub.1-C.sub.6-alkoxy, represents phenyl, phenyl-di-C.sub.4alkyl,
five- or six-membered hetaryl or five- or six-membered
hetaryl-C.sub.1-C.sub.4-alkyl, each of which is optionally mono- to
tetrasubstituted by halogen, C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.4-halogenoalkyl,
C.sub.1-C.sub.4-halogenoalkoxy, cyano or nitro, or represents the
groups 115 two adjacent Y.sub.n represent a 5- to 8-membered,
saturated or unsaturated cycle which may be interrupted by 1 to 3
heteroatoms from the group consisting of N, O, S and which may
optionally be mono- to trisubstituted by halogen,
C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy,
C.sub.1-C.sub.4-halogenoalkyl, C.sub.1-C.sub.4-halogenoalkoxy,
cyano or nitro, and Z represents hydrogen, represents in each case
optionally fluorine- and/or chlorine-substituted
C.sub.1-C.sub.8-alkyl, cyano-C.sub.1-C.sub.6-alkyl,
C.sub.3-C.sub.8-alkenyl, C.sub.3-C.sub.8-alkinyl,
C.sub.3-C.sub.8-cycloalkyl,
C.sub.3-C.sub.8-cycloalkyl-C.sub.1-C.sub.2-alkyl,
C.sub.1-C.sub.4-alkoxy-- C.sub.1-C.sub.4-alkyl,
C.sub.1-C.sub.4-halogenoalkoxy-C.sub.1-C.sub.4-alky- l, represents
phenoxy-C.sub.1-C.sub.4-alkyl, phenyl-C.sub.1-C.sub.4-alkylo-
xy-C.sub.1-C.sub.4-alkyl, phenylthio-C.sub.1-C.sub.4-alkyl,
phenyl-C.sub.1-C.sub.4-alkylthio-C.sub.1-C.sub.4-alkyl, phenyl,
phenyl-C.sub.1-C.sub.4-alkyl, five- or six-membered hetaryl, five-
or six-membered hetaryl-C.sub.1-C.sub.4-alkyl, each of which is
optionally mono- to tetrasubstituted by halogen,
C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.4-halogenoalkyl, C.sub.1-C.sub.4-halogeno-alkoxy,
nitro or cyano, or represents the groups 116 or cyano, g represents
0 to 2, l represents 0 to 2, R.sup.1 represents hydrogen (but not
for the radicals --CO.sub.2R.sup.1 and --SO.sub.2R.sup.1),
represents in each case fluorine- and/or chlorine-substituted
C.sub.1-C.sub.10-alkyl, C.sub.2-C.sub.10-alkenyl,
C.sub.3-C.sub.6-alkinyl, represents in each case optionally
fluorine-, chlorine-, C.sub.1-C.sub.4-alkyl-,
C.sub.1-C.sub.4-alkoxy-substituted C.sub.3-C.sub.8-cycloalkyl or
C.sub.5-C.sub.8-cycloalkenyl in which optionally one methylene
group may be interrupted by oxygen or sulphur, or represents
phenyl, pyridyl, thienyl, pyrimidyl, thiazolyl,
phenyl-C.sub.1-C.sub.4-alkyl, pyridyl-C.sub.1-C.sub.2-alkyl,
thiazolyl-C.sub.1-C.sub.2-alkyl, each of which is optionally mono-
to tetrasubstituted by halogen, C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.4-halogenoalkyl,
C.sub.1-C.sub.4-halogenoalkoxy, cyano or nitro, R.sup.2 represents
hydrogen, represents in each case optionally, fluorine- and/or
chlorine-substituted C.sub.1-C.sub.6-alkyl,
C.sub.3-C.sub.6-alkenyl, C.sub.3-C.sub.6-alkinyl,
C.sub.1-C.sub.6-alkoxy, C.sub.3-C.sub.6-alkenylo- xy or represents
phenyl, phenyl-C.sub.1-C.sub.4-alkyl or
phenyl-C.sub.1-C.sub.4-alkoxy, each of which is optionally mono- to
tetrasubstituted by halogen, C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.4-halogenoalkyl,
C.sub.1-C.sub.4-halogenoalkoxy, cyano or nitro, or R.sup.1, R.sup.2
together with the nitrogen atom to which they are attached
represent an optionally C.sub.1-C.sub.4-alkyl-substituted five- to
eight-membered cycle in which optionally one methylene group may be
replaced by oxygen or sulphur, R.sup.3 represents hydrogen,
optionally halogen-substituted C.sub.1-C.sub.6-alkyl or represents
phenyl or phenyl-C.sub.1-C.sub.2-alky- l each of which is
optionally mono- to tetrasubstituted by halogen,
C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.4-halogenoal- kyl, C.sub.1-C.sub.4-halogenoalkoxy,
cyano or nitro, R.sup.4 represents hydrogen or
C.sub.1-C.sub.6-alkyl, R.sup.5, R.sup.6 independently of one
another each represent hydrogen or optionally fluorine- and/or
chlorine-substituted C.sub.1-C.sub.4-alkyl, R.sup.7 represents in
each case optionally fluorine- and/or chlorine-substituted
C.sub.1-C.sub.10-alkyl, C.sub.2-C.sub.10-alkenyl,
C.sub.3-C.sub.10-alkiny- l, C.sub.1-C.sub.10-alkoxy,
C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.4-alkyl,
C.sub.1-C.sub.4-alkylthio-C.sub.1-C.sub.4-alkyl, in each case
optionally fluorine- and/or chlorine-, C.sub.1-C.sub.4-alkyl-,
C.sub.1-C.sub.4-alkoxy-substituted C.sub.3-C.sub.8-cycloalkyl or
C.sub.3-C.sub.8-cycloalkyloxy in which optionally one methylene
group may be replaced by oxygen or sulphur, represents phenyl,
phenoxy, benzyloxy, five- or six-membered hetaryl or
phenyl-C.sub.1-C.sub.4-alkyl, each of which is optionally mono- to
tetrasubstituted by halogen, C.sub.1-C.sub.6-alcyl,
C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.4-halogeno-a- lkyl,
C.sub.1-C.sub.4-halogenoalkoxy, cyano or nitro, or, in the case of
the radicals a) and c) mentioned under Ar, also represents a group
117 or, for the radical g), also represents hydroxyl, R.sup.8
represents hydrogen or C.sub.1-C.sub.4-alkyl, R.sup.9 represents
hydrogen, in each case optionally fluorine- and/or
chlorine-substituted C.sub.1-C.sub.10-alkyl,
C.sub.3-C.sub.8-alkenyl, C.sub.3-C.sub.8-alkinyl,
C.sub.1-C.sub.10-alkoxy, C.sub.3-C.sub.8-alkenyl-oxy, optionally
fluorine-, chlorine-, C.sub.1-C.sub.4-alkyl- or
C.sub.1-C.sub.4-alkoxy-su- bstituted C.sub.3-C.sub.8-cycloalkyl in
which optionally one methylene group may be replaced by oxygen or
sulphur, represents phenyl, phenyl-C.sub.1-C.sub.4-alkyl or
phenyl-C.sub.1-C.sub.2-alkoxy, each of which is optionally mono- to
tetrasubstituted by halogen, C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.4-halogenoal- kyl,
C.sub.1-C.sub.4-halogenoalkoxy, cyano or nitro, R.sup.10 represents
hydrogen, C.sub.1-C.sub.6-alkyl or C.sub.3-C.sub.6-alkenyl, or
R.sup.9, R.sup.10 together with the nitrogen atom to which they are
attached represent an optionally C.sub.1-C.sub.4-alkyl-substituted
five- to eight-membered cycle m which optionally one methylene
group may be replaced by oxygen or sulphur, and m represents 1 to
3, and n depending on m, represents 0 to 3.
3. Compounds according to claim 1, characterized in that K
represents oxygen or sulphur, Ar represents Ar.sup.1, where
Ar.sup.1 represents phenyl, naphthyl, quinolinyl, thienyl,
pyrimidyl, furanyl, thiazolyl, benzothiazolyl, oxazolyl, pyrazolyl
or pyridyl, each of which is optionally mono- to trisubstituted by
fluorine, chlorine, bromine, C.sub.1-C.sub.6-alkyl,
C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkinyl,
C.sub.1-C.sub.6-alkoxy, C.sub.3-C.sub.6-alkenyloxy,
C.sub.3-C.sub.6-alkinyloxy, C.sub.1-C.sub.6-alkylthio,
C.sub.1-C.sub.4-alkylsulfinyl, C.sub.1-C.sub.4-alkylsulfonyl,
C.sub.1-C.sub.4-halogenoalkyl, C.sub.1-C.sub.4-halogeno-alkoxy,
C.sub.2-C.sub.4-halogenoalkenyloxy,
C.sub.1-C.sub.2-alkylidenediyl-dioxy,
C.sub.1-C.sub.2-halogenoalkylidenediyl-dioxy,
halogeno-C.sub.1-C.sub.2-al- kylthio,
halogeno-C.sub.1-C.sub.2-alkylsulfinyl, halogeno-C.sub.1-C.sub.2--
alkylsulfonyl, hydroxyl, mercapto, nitro, cyano, amino or by one of
the following groups 118 or represents Ar.sup.2, where Ar.sup.2
represents Ar.sup.1 which is additionally substituted by phenyl,
pyridyl, pyrimidyl, thienyl, furanyl, thiazolyl, tetrazolyl,
triazolyl, benzyl, phenoxy, phenyl-S(O).sub.g--, pyridyloxy,
pyrimidyloxy, thiazolyloxy, pyridyl-S(O).sub.g--,
pyrimidyl-S(O).sub.g-- or thiazolyl-S(O).sub.g--, where these
substituents for their part are optionally mono- to tri-substituted
by fluorine, chlorine, bromine, C.sub.1-C.sub.4-alkyl,
C.sub.2-C.sub.4-alkenyl, C.sub.1-C.sub.4-alkoxy,
C.sub.1-C.sub.2-halogeno- alkyl, C.sub.1-C.sub.2-halogenoalkoxy,
nitro or cyano, where g represents 0 to 2, and L represents oxygen
or sulphur, X represents CN, 119Y represents fluorine,
C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.2-halogenoalkyl- ,
C.sub.1-C.sub.4-alkoxy, represents phenyl,
phenyl-C.sub.1-C.sub.2-alkyl, thiazolylmethyl, pyridylmethyl, each
of which is optionally mono- to trisubstituted by fluorine,
chlorine, bromine, C.sub.1-C.sub.4-allyl, C.sub.1-C.sub.4-alkoxy,
C.sub.1-C.sub.2-halogenoalkyl, C.sub.1-C.sub.2-halogenoalkoxy,
cyano or nitro, or represents the groups --CO.sub.2R.sup.1 or 120
two adjacent Y.sub.n furthermore represent a 5- to 6-membered,
saturated or unsaturated cycle which may be interrupted by a
heteroatom from the group consisting of N, O, S and which may
optionally be mono- to disubstituted by fluorine, chlorine,
bromine, methyl, t-butyl, methoxy, trifluoromethyl,
trifluoromethoxy, cyano or nitro, and Z represents hydrogen,
represents in each case optionally fluorine- and/or
chlorine-substituted C.sub.1-C.sub.6-alkyl,
cyano-C.sub.1-C.sub.3-alkyl, C.sub.3-C.sub.6-alkenyl,
C.sub.3-C.sub.8-alkinyl, C.sub.3-C.sub.6-cycloalkyl,
C.sub.3-C.sub.6-cycloalkyl-C.sub.1-C.sub.2-alkyl,
C.sub.1-C.sub.4-alkoxy-- C.sub.1-C.sub.2-alkyl,
C.sub.1-C.sub.4-halogeno-C.sub.1-C.sub.2-alkyl, represents
phenoxy-C.sub.1-C.sub.2-alkyl, phenyl-C.sub.1-C.sub.2-alkyloxy-
-C.sub.1-C.sub.2-alkyl, phenylthio-C.sub.1-C.sub.2-alkyl,
phenyl-C.sub.1-C.sub.2-alkylthio-C.sub.1-C.sub.2-alkyl,
phenyl-C.sub.1-C.sub.2-alkyl, phenyl,
pyridyl-C.sub.1-C.sub.2-alkyl, thiazolyl-C.sub.1-C.sub.2-alkyl,
each of which is optionally mono- to trisubstituted by fluorine,
chlorine, bromine, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy,
C.sub.1-C.sub.2-halogenoalkyl, C.sub.1-C.sub.2-halogenoalkoxy,
nitro or cyano, or represents the groups 121 or cyano, l represents
0 to 1, R.sup.1 represents hydrogen (but not for the radicals
--CO.sub.2R.sub.1 and O.sub.2R.sup.1), represents in each case
optionally fluorine- and/or chlorine-substituted
C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.3-C.sub.4-alkinyl, represents optionally fluorine-,
chlorine-, C.sub.1-C.sub.2-alkyl-,
C.sub.1-C.sub.2-alkoxy-substituted C.sub.3-C.sub.6-cycloalkyl or
represents phenyl or benzyl, 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-halogenoalkyl, C.sub.1-C.sub.2-halogenoalkoxy,
cyano or nitro, R.sup.2 represents hydrogen, represents in each
case optionally fluorine- and/or chlorine-substituted
C.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.4-alkenyl,
C.sub.3-C.sub.4-alkinyl, C.sub.1-C.sub.4-alkoxy,
C.sub.3-C.sub.4-alkenylo- xy or represents phenyl, benzyl or
benzyloxy, 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-halogenoal- kyl,
C.sub.1-C.sub.2-halogenoalkoxy, cyano or nitro, or R.sup.1, R.sup.2
together with the nitrogen atom to which they are attached
represent an optionally C.sub.1-C.sub.2-alkyl-substituted five- or
six-membered cycle in which optionally one methylene group may be
replaced by oxygen, R.sup.3 represents hydrogen, represents
C.sub.1-C.sub.4-alkyl or represents phenyl or benzyl, 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,
trifluoromethyl, difluoromethoxy, trifluoromethoxy, cyano or nitro,
R.sup.4, R.sup.5, R.sup.6 each represents hydrogen, methyl or
ethyl, R.sup.7 represents in each case optionally fluorine- and/or
chlorine-substituted C.sub.1-C.sub.6-alkyl,
C.sub.2-C.sub.6-alkenyl, C.sub.3-C.sub.6-alkinyl,
C.sub.1-C.sub.6-alkoxy,
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, in each case
optionally fluorine- and/or chlorine-, C--C.sub.2-alkyl-,
C.sub.1-C.sub.2-alkoxy-substituted C.sub.3-C.sub.6-cycloalkyl in
which optionally one methylene group may be replaced by oxygen,
represents phenyl, phenoxy, benzyloxy, thienyl, furanyl, pyridyl,
pyrimidyl, thiazolyl, pyrazolyl 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,
trifluoromethyl, difluoromethoxy, trifluoromethoxy, cyano or nitro,
or, in the case of the radicals a) and c) mentioned under Ar, also
represents a group 122 for the radical g), also represents
hydroxyl, R.sup.8 represents hydrogen, R.sup.9 represents hydrogen,
in each case optionally fluorine- and/or chlorine-substituted
C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-alkenyl,
C.sub.3-C.sub.6-alkinyl, C.sub.1-C.sub.6-alkoxy,
C.sub.3-C.sub.6-cycloalkyl, in which optionally one methylene group
may be replaced by oxygen, 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, trifluoromethyl,
difluoromethoxy, trifluoromethoxy, cyano or nitro, R.sup.10
represents hydrogen or C.sub.1-C.sub.4-alkyl, or R.sup.9, R.sup.10
together with the nitrogen atom to which they are attached
represent an optionally C.sub.1-C.sub.2-alkyl-substituted five- to
six-membered cycle in which optionally one methylene group may be
replaced by oxygen, and m represents 0 to 1, and n depending on m,
represents 0 to 2.
4. Compounds according to claim 1, characterized in that K
represents oxygen or sulphur, Ar represents Ar.sup.1, where
Ar.sup.1 represents phenyl, thienyl, pyrimidyl, furanyl or pyridyl,
each of which is optionally mono- to trisubstituted by fluorine,
chlorine, bromine, methyl, ethyl, propyl, i-propyl, s-, n-, i- or
t-butyl, methoxy, ethoxy, propoxy, i-propoxy, s-, n-, i- or
t-butoxy, allyloxy, methallyloxy, 2-butenyloxy, propargyloxy,
2-butinyloxy, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl,
methylsulfonyl, ethylsulfonyl, trifluoromethyl, difluoromethoxy,
trifluoromethoxy, methylenedioxy, difluoromethylenedioxy,
tetrafluoroethylenedioxy, difluoromethylthio, trifluoromethylthio,
trifluoromethylsulfinyl, trifluoromethylsulfonyl, hydroxyl,
mercapto, nitro, cyano, amino or by one of the following groups 123
or represents Ar.sup.2, where Ar.sup.2 represents Ar.sup.1 which is
additionally substituted by phenyl, pyridyl, thienyl, tetrazolyl,
triazolyl or phenoxy, where these substituents for their part are
optionally mono- to disubstituted by fluorine, chlorine, bromine,
methyl, ethyl, n- or i-propyl, s-, n-, i- or t-butyl, methoxy,
ethoxy, i-propoxy, s-, n- or t-butoxy, trifluoromethyl,
trifluoromethoxy, nitro or cyano, and L represents oxygen or
sulphur, X represents --CN, --CO--NH.sub.2, 124Y represents methyl,
phenyl which is optionally mono- to trisubstituted by fluorine,
chlorine, bromine, methyl, methoxy, trifluoromethyl or
trifluoromethoxy, or represents the group --CO.sub.2R.sup.1, or two
adjacent Y.sub.n represent a six-membered unsaturated cycle which
may optionally be monosubstituted by fluorine, chlorine, bromine,
methyl, methoxy, trifluoromethyl, trifluoromethoxy, cyano or nitro,
and Z represents hydrogen, methyl, ethyl, allyl, propargyl,
cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl,
cyclopentylmethyl, cyclohexylmethyl, methoxymethyl, ethoxymethyl,
represents phenyl, benzyl, pyridylmethyl, thiazolylmethyl, each of
which is optionally mono- to disubstituted by fluorine, chlorine,
bromine, methyl, methoxy, trifluoromethyl or trifluoromethoxy,
cyano or nitro, or represents the groups 125 or cyano, R.sup.1
represents hydrogen (but not for the radicals O.sub.2R.sup.1 and
--SO.sub.2R.sup.1), methyl, ethyl, propyl, isopropyl, n-, s-, i- or
t-butyl, allyl, propargyl, cyclopropyl, cyclopentyl, cyclohexyl,
represents phenyl or benzyl, each of which is optionally mono- to
disubstituted by fluorine, chlorine, bromine, methyl, methoxy,
trifluoromethyl, trifluoromethoxy, cyano or nitro, R.sup.2
represents hydrogen, methyl, ethyl, propyl, isopropyl, allyl,
propargyl, methoxy, ethoxy, allyloxy or represents benzyloxy which
is optionally mono- to disubstituted by fluorine, chlorine,
bromine, methyl, methoxy, trifluoromethyl, trifluoromethoxy, cyano
or nitro, or R.sup.1, R.sup.2 together with the nitrogen atom to
which they are attached represent a pyrrolidine, piperidine,
thiazine or morpholine radical, R.sup.3, R.sup.5 each represent
hydrogen, methyl or ethyl, R.sup.7 represents methyl, ethyl,
propyl, isopropyl, n-, s-, i- or t-butyl, vinyl, trifluoromethyl,
methoxy, ethoxy, propoxy, isopropoxy, n-, s-, i- or t-butyloxy,
cyclopropyl, cyclopentyl, cyclohexyl, cyclopentyloxy,
cyclohexyloxy, represents phenyl, pyridyl or benzyl, each of which
is optionally mono- to disubstituted by fluorine, chlorine,
bromine, methyl, n-, s-, i- or t-butyl, methoxy, trifluoromethyl,
trifluoromethoxy, cyano or nitro, or, in the case of the radicals
a) and c) mentioned under Ar, also represents a group 126 , for the
radical g), also represents hydroxyl, R.sup.9 represents hydrogen,
methyl, ethyl, propyl, isopropyl, n-, s-, i- or t-butyl,
cyclopropyl, cyclopentyl, cyclohexyl, represents phenyl which is
optionally mono- to disubstituted by fluorine, chlorine, bromine,
methyl, methoxy, trifluoromethyl, trifluoromethoxy, cyano or nitro,
R.sup.10 represents hydrogen, methyl or ethyl, or R.sup.9, R.sup.10
together with the nitrogen atom to which they are attached
represent a pyrrolidine, piperidine or morpholine radical, and m
represents 1 to 3, and n depending on m, represents 0 to 1.
5. Compounds according to claim 1, characterized in that K
represents oxygen or sulphur, Ar represents Ar.sup.1, where
Ar.sup.1 represents phenyl, thienyl, pyrimidyl or pyridyl, each of
which is optionally mono- to trisubstituted by fluorine, chlorine,
bromine, methyl, ethyl, propyl, isopropyl, n-, s-, i- or t-butyl,
methoxy, ethoxy, propoxy, isopropoxy, tert-butoxy, allyloxy,
methallyloxy, 2-butenyloxy, propargyloxy, 2-butinyloxy, methylthio,
ethylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl,
ethylsulphonyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy,
methylenedioxy, difluoromethylenedioxy, tetrafluoroethylenedioxy,
difluoromethylthio, trifluoromethylthio, trifluoromethylsulphinyl,
trifluoromethylsulphonyl, hydroxyl, mercapto, nitro, cyano, amino,
or represents Ar.sup.2, where Ar.sup.2 represents Ar.sup.2 which is
additionally substituted by phenyl or phenoxy, where these
substituents for their part are optionally mono- to disubstituted
by fluorine, chlorine, bromine, methyl, ethyl, isopropyl, n-, s-,
i- or t-butyl, methoxy, ethoxy, isopropoxy, n-, s-, i- or t-butoxy,
trifluoromethyl, trifluoromethoxy, nitro or cyano, and X represents
CN, Z represents hydrogen or methyl, m represents 1 to 3, and n
represents 0.
6. Process for preparing compounds according to any of claims 1 to
5, characterized in that (A) in the case where K represents oxygen
and Z represents hydrogen, compounds of the formula (II) 127 in
which Ar and X are each as defined in any of claims 1 to 5, are
reacted with compounds of the formula (III) 128 in which Y, m, n
are each as defined in any of claims 1 to 5, and W represents O or
S(O).sub.g, where g represents 0 or 2, and R.sup.11 represents
alkyl or benzyl, if appropriate in the presence of a diluent and if
appropriate in the presence of a base or a metal compound of the
formula (IIIa) Me(V).sub.2 (IIIa) in which Me represents a divalent
transition metal atom and V represents a chelate ligand, or in that
(B) in the case where K represents oxygen and Z represents
hydrogen, compounds of the formula (IV) 129 in which Ar and X are
each as defined in any of claims 1 to 5 and Hal represents halogen,
are reacted with compounds of the formula (V) 130 in which Y, m and
n are each as defined in any of claims 1 to 5, if appropriate in
the presence of a diluent to give compounds of the formula (VI) 131
in which Ar, X, Y, m and n are each as defined in any of claims 1
to 5, which are reacted further, if appropriate in the presence of
a base and if appropriate in the presence of a trivalent phosphorus
compound, with elimination of sulphur and hydrogen halide, to give
compounds of the formula (I) in which Ar, X, Y, m and n are each as
defined in any of claims 1 to 5 and Z represents hydrogen, or that
(C) in the case where K represents oxygen and Z does not represent
hydrogen compounds of the formula (VII) 132 in which Y, m and n are
each as defined in any of claims 1 to 5, are reacted with
halogenating agents, if appropriate in the presence of a diluent,
to give compound of the formula (VIII) 133 in which Y, Z, m and n
are each as defined in any of claims 1 to 5 and Z does not
represent hydrogen, and Hal represents halogen, which are then
reacted with compounds of the formula (II) 134 in which Ar, X are
each as defined in any of claims 1 to 5, if appropriate in the
presence of a diluent and if appropriate in the presence of an acid
acceptor, or in that (D) in the case where K represents oxygen and
Z does not represent hydrogen, compounds of the formula (I-a) 135
in which Ar, X, Y, m and n are each as defined in. any of claims 1
to S are reacted with alkylating agents, acylating agents,
sulphonylating agents or condensing agents of the formula (IX) Z-G
(IX), in which G represents a leaving group such as halogen,
sulphonate or alkoxy, if appropriate in the presence of a solvent
and if appropriate in the presence of a base, or in that (E) in the
case where Ar represents Ar.sup.2 according to any of claims 1 to
5, compounds of the formula (I.sup.1) 136 in which Ar.sup.1, X, Y,
Z, m and n are each as defined in any of claims 1 to 5 and Hal
represents halogen, are reacted with boronic acids of the formula
(X) Ar.sup.2-B(OH).sub.2 (X), in which Ar.sup.2 is as defined in
any of claims 2 to 5, Ar.sup.2' represents the substituents which
were mentioned in claim 1 as additional substituents for Ar.sup.1,
in the presence of a solvent, if appropriate in the presence of a
base and/or a noble metal complex, or in that (F) compounds of the
formula (I) 137 in which Ar, X, Y, Z, m and n are each as defined
in any of claims 1 to 5, and K represents oxygen, are reacted in
the presence of a sulphurizing agent in the presnce of a solvent.
Herbicidal, acaricidal and/or insecticidal compositions,
characterized in that they comprise at least one compound according
to any of claims 1 to 5.
8. Use of compounds according to any of claims 1 to 5 for
controlling undesirable vegetation and/or animal pests.
9. Compounds of the formula (V) 138in which Y.sub.n represents
optionally substituted phenyl and m=1 or 2, except for the
compounds 5-phenyl-pyrrolidine-2-thione and
5-(3,4-dimethoxyphenyl)-pyrrolidine-2-t- hione.
10. Compounds of the formula (II-1-b) 139where T is as defined in
the table below:
16 T 3-Cl, 4-F 4-Cl, 3-F 3,5-(CF.sub.3).sub.2 2,4-Cl.sub.2, 5-F
3,5-Cl.sub.2, 4-F 4-Cl, 2-F 3-CF.sub.3, 5-CH.sub.3 3-Cl,
4,5-F.sub.2 4-CN, 2,5-F.sub.2 2,3-F.sub.2 3-F, 4-CF.sub.3
3,4-O--CF.sub.2--O 3-NO.sub.2, 5-CF.sub.3 4-Cl, 2,5-F.sub.2
3,4,5-(OC.sub.2H.sub.5).sub.3 4-Br, 2-F 2,6-Cl.sub.2, 4-CF.sub.3
2-F, 4-NO.sub.2 2,4-Cl.sub.2, 5-NO.sub.2 4-Cl, 2-F, 5-NO.sub.2
2,4-F.sub.2, 5-NO.sub.2 4-Br, 2-F, 5-NO.sub.2 2-F, 4-CF.sub.3
4-OCF.sub.3, 3-NO.sub.2 4-Cl, 2-NO.sub.2 2-F, 3-CF.sub.3 2-Cl, 6-F
2-Cl, 3-CF.sub.3 3,4-O--(CF.sub.2).sub.2--O-- 2-Cl, 4-SCH.sub.3
2-Cl, 4-SO.sub.2CH.sub.3
11. Compounds of the formula (II-2-b) 140where T is as defined in
the table below:
17 T 2,6-Cl.sub.2 2,6-Cl.sub.2, 4-CH.sub.3 6-Cl
Description
[0001] The invention relates to novel phenyl-substituted cyclic
enaminones, to a plurality of processes for their preparation, to
intermediates and to the use of the enaminones as crop protection
agents, in particular as herbicides, acaricides, nematicides and
insecticides.
[0002] Certain cyclic enaminones which are substituted in the
phenyl ring have already been disclosed as intermediates for
antibacterial quinolones (R. G. Glushkov, N. B. Marchenko, A. N.
Padeiskaya, L. D. Shipilova, Pharm. Chem. J. (Engl. Transl.) 24,
460-465, (1990)). Furthermore, cyclic enaminones which are not
substituted in the phenyl ring have been disclosed (M. V.
Mezentseva, A. V. Kadushkin, L. M. Alekseeva, A. S. Sokolova, V. G.
Granik, Pharm. Chem. J. (Engl. Transl.) 25, 858-864 (1991); G. M.
Coppola, R. Damon, A. D. Kahle, M. J. Shapiro, J. Org. Chem. 46,
1221-1222, (1981); D. Brillon, G. Sauv, J. Org. Chem. 55,
2246-2249, (1990)). A use of these compounds as crop protection
agents has not yet been described.
[0003] The novel cyclic enaminones are described in a general
manner by the formula (I) 2
[0004] in which
[0005] K represents oxygen or sulphur,
[0006] Ar represents in each case substituted phenyl, naphthyl or
represents in each case optionally substituted mono- or bicyclic
hetaryl having 5 to 10 ring atoms,
[0007] X represents CN, 3
[0008] Y represents halogen or in each case optionally substituted
alkyl, alkoxy, phenyl, phenylalkyl, hetaryl, hetarylalkyl or
represents the groups 4
[0009] two adjacent Y.sub.n furthermore represent an optionally
substituted saturated or unsaturated cycle which may optionally be
interrupted by heteroatoms, and
[0010] Z represents hydrogen, represents in each case optionally
substituted alkyl, alkenyl, alkinyl, cycloalkyl, cycloalkyl-alkyl,
alkoxyalkyl, phenoxyalkyl, phenylalkyl-oxyalkyl, phenylthioalkyl,
phenylalkyl-thioalkyl, phenyl, phenylalkyl, hetaryl, hetaryl-alkyl
or represents the groups 5
[0011] or cyano,
[0012] l represents 0 to 3,
[0013] m represents 1 to 3,
[0014] n represents, depending on m, 0 to 4,
[0015] R.sup.1 represents hydrogen, represents in each case
optionally substituted, saturated or unsaturated alkyl or
cycloalkyl, each of which is optionally interrupted by heteroatoms,
represents in each case optionally substituted phenyl or hetaryl,
represents in each case optionally substituted phenylalkyl or
hetarylalkyl,
[0016] R.sup.2 represents hydrogen, represents in each case
optionally substituted, saturated or unsaturated alkyl or alkoxy,
represents in each case optionally substituted phenyl, phenylalkyl
or phenylaluyloxy, or
[0017] R.sup.1, R.sup.2 together with the nitrogen atom to which
they are attached may furthermore represent an optionally
substituted cycle which is optionally interrupted by
heteroatoms,
[0018] R.sup.3 represents hydrogen, represents in each case
optionally substituted alkyl or alkoxy, represents in each case
optionally substituted phenyl or phenylalkyl,
[0019] R.sup.4 represents hydrogen or represents optionally
substituted alkyl, and
[0020] R.sup.5, R.sup.6 independently of one another represent
hydrogen or represent optionally substituted alkyl.
[0021] Compounds of the following formula: 6
[0022] are excluded.
[0023] For the compounds of the formula (I), the following
applies:
[0024] Ar preferably represents Ar.sup.1, where Ar.sup.1 represents
phenyl, naphthyl or mono- or bicyclic hetaryl having five to ten
ring atoms, each of which radicals is optionally mono- to
pentasubstituted by halogen, C.sub.1-C.sub.8-alkyl,
C.sub.2-C.sub.8-alkenyl, C.sub.2-C.sub.8-alkinyl,
C.sub.1-C.sub.8-alkoxy, C.sub.2-C.sub.8-alkenylo- xy,
C.sub.3-C.sub.8-alkinyloxy, C.sub.1-C.sub.8-alkylthio,
C.sub.1-C.sub.6-alkylsulphinyl, C.sub.1-C.sub.6-alkylsulphonyl,
C.sub.1-C.sub.6-halogenoalkyl, C.sub.1-C.sub.6-halogenoalkoxy,
C.sub.2-C.sub.8-halogenoalkenyloxy,
C.sub.1-C.sub.2-alkylidenediyl-dioxy,
C.sub.1-C.sub.2-halogenoalkylidenediyl-dioxy,
halogeno-C.sub.1-C.sub.4-al- kylthio,
halogeno-C.sub.1-C.sub.4-alkylsulphinyl, halogeno-C.sub.1-C.sub.4-
-alkylsulphonyl, hydroxyl, mercapto, nitro, cyano, amino, or by the
groups 7
[0025] or represents Ar.sup.2, where Ar.sup.2 represents Ar.sup.1
which is additionally substituted by phenyl, naphthyl, five- or
six-membered hetaryl, phenyl-C.sub.1-C.sub.4-alkyl, phenoxy,
phenyl-S(O).sub.g--, five- or six-membered hetaryloxy or
hetaryl-S(O).sub.g, where these substituents for their part are in
each case optionally mono- to tetrasubstituted by halogen,
C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.4-halogenoalkyl, C.sub.1-C.sub.4-halogenoalkoxy,
nitro or cyano.
[0026] K preferably represents oxygen or sulphur.
[0027] L preferably represents oxygen or sulphur.
[0028] X preferably represents CN, 8
[0029] Y preferably represents halogen, C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.4-halogenoalkyl, C.sub.1-C.sub.6-alkoxy, represents
phenyl, phenyl-C.sub.1-C.sub.4-alkyl, five- or six-membered hetaryl
or five- or six-membered hetaryl-C.sub.1-C.sub.4-alkyl, each of
which is optionally mono- to tetrasubstituted by halogen,
C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.4-halogenoalkyl, C.sub.1-C.sub.4-halogenoalkoxy,
cyano or nitro, or represents the groups 9
[0030] Two adjacent Y.sub.n preferably represent a 5- to
8-membered, saturated or unsaturated cycle which may be interrupted
by 1 to 3 heteroatoms from the group consisting of N, O, S and
which may optionally be mono- to trisubstituted by halogen,
C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy,
C.sub.1-C.sub.4-halogenoalkyl, C.sub.1-C.sub.4-halogenoalkoxy,
cyano or nitro.
[0031] Z preferably represents hydrogen, represents in each case
optionally fluorine- and/or chlorine-substituted
C.sub.1-C.sub.8-alkyl, cyano-C.sub.1-C.sub.6-alkyl,
C.sub.3-C.sub.8-alkenyl, C.sub.3-C.sub.8-alkinyl,
C.sub.3-C.sub.8-cycloallyl,
C.sub.3-C.sub.8-cycloalkyl-C.sub.1-C.sub.2-alkyl,
C.sub.1-C.sub.4-alkoxy-- C.sub.1-C.sub.4-alkyl,
C.sub.1-C.sub.4-halogenoalkoxy-C.sub.1-C.sub.4-alky- l, represents
phenoxy-C.sub.1-C.sub.4-alkyl, phenyl-C.sub.1-C.sub.4-alkylo-
xy-C.sub.1-C.sub.4-alkyl, phenylthio-C.sub.1-C.sub.4-alkyl,
phenyl-C.sub.1-C.sub.4-alylthio-C.sub.1-C.sub.4-alkyl, phenyl,
phenyl-C.sub.1-C.sub.4-allyl, five- or six-membered hetaryl, five-
or six-membered hetaryl-C.sub.1-C.sub.4-alkyl, each of which is
optionally mono- to tetrasubstituted by halogen,
C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.4-halogenoalkyl, C.sub.1-C.sub.4-halogenoalkoxy,
nitro or cyano, or represents the groups 10
[0032] or cyano, where
[0033] g preferably represents 0 to 2,
[0034] l preferably represents 0 to 2,
[0035] R.sup.1 preferably represents hydrogen (but not for the
radicals --CO.sub.2R.sup.1 and --SO.sub.2R.sup.1), represents in
each case optionally fluorine- and/or chlorine-substituted
C.sub.1-C.sub.10-alkyl, C.sub.2-C.sub.10-alkenyl,
C.sub.3-C.sub.6-alkinyl, represents in each case optionally
fluorine-, chlorine-, C.sub.1-C.sub.4-alkyl-,
C.sub.1-C.sub.4-alkoxy-substituted C.sub.3-C.sub.8-cycloalkyl or
C.sub.5-C.sub.8-cycloalkenyl in which optionally one methylene
group may be interrupted by oxygen or sulphur, or represents
phenyl, pyridyl, thienyl, pyrimidyl, thiazolyl,
phenyl-C.sub.1-C.sub.4-alkyl, pyridyl-C.sub.1-C.sub.2-alkyl,
thiazolyl-C.sub.1-C.sub.2-alkyl, each of which is optionally mono-
to tetrasubstituted by halogen, C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.4-halogenoal- kyl,
C.sub.1-C.sub.4-halogenoalkoxy, cyano or nitro,
[0036] R.sup.2 preferably represents hydrogen, represents in each
case optionally fluorine- and/or chlorine-substituted
C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-alkenyl,
C.sub.3-C.sub.6-alkinyl, C.sub.1-C.sub.6-alkoxy,
C.sub.3-C.sub.6-alkenyloxy or represents phenyl,
phenyl-C.sub.1-C.sub.4-a- lkyl or phenyl-C.sub.1-C.sub.4-alkoxy,
each of which is optionally mono- to tetrasubstituted by halogen,
C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.4-halogenoalkyl, C.sub.1-C.sub.4-halogeno-alkoxy,
cyano or nitro,
[0037] R.sup.1,R.sup.2 together with the nitrogen atom to which
they are attached furthermore preferably represent an in each case
optionally C.sub.1-C.sub.4-alkyl-substituted five- to
eight-membered cycle in which optionally one methylene group may be
replaced by oxygen or sulphur,
[0038] R.sup.3 preferably represents hydrogen, optionally
halogen-substituted C.sub.1-C.sub.6-alkyl or represents phenyl or
phenyl-C.sub.1-C.sub.2-alkyl each of which is optionally mono- to
tetrasubstituted by halogen, C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.4-halogenoalkyl,
C.sub.1-C.sub.4-halogenoalkoxy, cyano or nitro,
[0039] R.sup.4 preferably represents hydrogen or
C.sub.1-C.sub.6-alkyl,
[0040] R.sup.5, R.sup.6 independently of one another each
preferably represent hydrogen or optionally fluorine- and/or
chlorine-substituted C.sub.1-C.sub.4-alkyl,
[0041] R.sup.7 preferably represents in each case optionally
fluorine- and/or chlorine-substituted C.sub.1-C.sub.10-allyl,
C.sub.2-C.sub.10-alkenyl, C.sub.3-C.sub.10-alkinyl,
C.sub.1-C.sub.10-alkoxy,
C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.4-alkyl,
C.sub.1-C.sub.4-alkylthio-C.sub.1-C.sub.4-alkyl, in each case
optionally fluorine- and/or chlorine-, C.sub.1-C.sub.4-alkyl-,
C.sub.1-C.sub.4-alkoxy-substituted C.sub.3-C.sub.8-cycloalkyl or
C.sub.3-C.sub.8-cycloalkyloxy in which optionally one methylene
group may be replaced by oxygen or sulphur, represents phenyl,
phenoxy, benzyloxy, five- or six-membered hetaryl or
phenyl-C.sub.1-C.sub.4-alkyl, each of which is optionally mono- to
tetrasubstituted by halogen, C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.4-halogeno-a- lkyl,
C.sub.1-C.sub.4-halogenoalkoxy, cyano or nitro, or, in the case of
the radicals a) and c) mentioned under Ar, also represents a group
11
[0042] for the radical g), also represents hydroxyl,
[0043] R.sup.8 preferably represents hydrogen or
C.sub.1-C.sub.4-alkyl,
[0044] R.sup.9 preferably represents hydrogen, in each case
optionally fluorine- and/or chlorine-substituted
C.sub.1-C.sub.10-alkyl, C.sub.3-C.sub.8-alkenyl,
C.sub.3-C.sub.8-alkinyl, C.sub.1-C.sub.10-alkoxy- ,
C.sub.3-C.sub.8-alkenyloxy, optionally fluorine-, chlorine-,
C.sub.1-C.sub.4-alkyl- or C.sub.1-C.sub.4-alkoxy-substituted
C.sub.3-C.sub.8-cycloalkyl in which optionally one methylene group
may be replaced by oxygen or sulphur, represents phenyl,
phenyl-C.sub.1-C.sub.4-- alkyl or phenyl-C.sub.1-C.sub.2-alkoxy,
each of which is optionally mono- to tetrasubstituted by halogen,
C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.4-halogenoalkyl, C.sub.1-C.sub.4-halogenoalkoxy,
cyano or nitro,
[0045] R.sup.10 preferably represents hydrogen,
C.sub.1-C.sub.6-alkyl or C.sub.3-C.sub.6-alkenyl,
[0046] R.sup.9, R.sup.10 together with the nitrogen atom to which
they are attached preferably furthermore represent an optionally
C.sub.1-C.sub.4-alkyl-substituted five- to eight-membered cycle in
which optionally one methylene group may be replaced by oxygen or
sulphur.
[0047] m preferably represents 1 to 3.
[0048] n depending on m, preferably represents 0 to 3.
[0049] K particularly preferably represents oxygen or sulphur.
[0050] Ar particularly preferably represents Ar.sup.1, where
Ar.sup.1 represents phenyl, naphthyl, quinolinyl, thienyl,
pyrimidyl, furanyl, thiazolyl, benzothiazolyl, oxazolyl, pyrazolyl
or pyridyl, each of which is optionally mono- to tri-substituted by
fluorine, chlorine, bromine, C.sub.1-C.sub.6-alkyl,
C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkinyl,
C.sub.1-C.sub.6-alkoxy, C.sub.3-C.sub.6-alkenyloxy,
C.sub.3-C.sub.6-alcinyloxy, C.sub.1-C.sub.6-alkylthio,
C.sub.1-C.sub.4-alkylsulphinyl, C.sub.1-C.sub.4-alkylsulphonyl,
C.sub.1-C.sub.4-halogenoalkyl, C.sub.1-C.sub.4-halogeno-alkoxy,
C.sub.2-C.sub.4-halogenoalkenyloxy,
C.sub.1-C.sub.2-alkylidenediyl-dioxy,
C.sub.1-C.sub.2-halogenoalkylidenediyl-dioxy,
halogeno-C.sub.1-C.sub.2-al- kylthio,
halogeno-C.sub.1-C.sub.2-alkylsulphinyl, halogeno-C.sub.1-C.sub.2-
-alkylsulphonyl, hydroxyl, mercapto, nitro, cyano, amino or by one
of the following groups 12
[0051] or represents Ar.sup.2, where Ar.sup.2 represents Ar.sup.1
which is additionally substituted by phenyl, pyridyl, pyrimidyl,
thienyl, furanyl, thiazolyl, tetrazolyl, triazolyl, benzyl,
phenoxy, phenyl-S(O).sub.g--, pyridyloxy, pyrimidyloxy,
thiazolyloxy, pyridyl-S(O).sub.g--, pyrimidyl-S(O).sub.g-- or
thiazolyl-S(O).sub.g--, where these substituents for their part are
optionally mono- to tri-substituted by fluorine, chlorine, bromine,
C.sub.1-C.sub.4-alkyl, C.sub.2-C.sub.4-alkenyl,
C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.2-halogeno- alkyl,
C.sub.1-C.sub.2-halogenoalkoxy, nitro or cyano, where g represents
0 to 2.
[0052] L particularly preferably represents oxygen or sulphur.
[0053] X particularly preferably represents CN, 13
[0054] Y particularly preferably represents fluorine.
C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.2-halogenoalkyl,
C.sub.1-C.sub.4-alkoxy, represents phenyl,
phenyl-C.sub.1-C.sub.2-alkyl, thiazolylmethyl, pyridylmethyl, each
of which is optionally mono- to trisubstituted by fluorine,
chlorine, bromine, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy,
C.sub.1-C.sub.2-halogenoalkyl, C.sub.1-C.sub.2-halogenoalkoxy,
cyano or nitro, or represents the groups
[0055] --CO.sub.2R.sup.1 or 14
[0056] Two adjacent Y.sub.n may furthermore particularly preferably
represent a 5- to 6-membered, saturated or unsaturated cycle which
may be interrupted by a heteroatom from the group consisting of N,
O, S and which may optionally be mono- to disubstituted by
fluorine, chlorine, bromine, methyl, t-butyl, methoxy,
trifluoromethyl, trifluoromethoxy, cyano or nitro.
[0057] Z particularly preferably represents hydrogen, represents in
each case optionally fluorine- and/or chlorine-substituted
C.sub.1-C.sub.6-alkyl, cyano-C.sub.1-C.sub.3-allyl,
C.sub.3-C.sub.6-alkenyl, C.sub.3-C.sub.8-alkinyl,
C.sub.3-C.sub.6-cycloal- kyl,
C.sub.3-C.sub.6-cycloalkyl-C.sub.1-C.sub.2-alkyl,
C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.2-alkyl,
C.sub.1-C.sub.4-halogeno-C.- sub.1-C.sub.2-alkyl, represents
phenoxy-C.sub.1-C.sub.2-alkyl,
phenyl-C.sub.1-C.sub.2-alkyloxy-C.sub.1-C.sub.2-alkyl,
phenylthio-C.sub.1-C.sub.2-alkyl,
phenyl-C.sub.1-C.sub.2-alkylthio-C.sub.- 1-C.sub.2-alkyl,
phenyl-C.sub.1-C.sub.2-alkyl, phenyl,
pyridyl-C.sub.1-C.sub.2-alkyl, thiazolyl-C.sub.1-C.sub.2-alkyl,
each of which is optionally mono- to trisubstituted by fluorine,
chlorine, bromine, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy,
C.sub.1-C.sub.2-halogenoalkyl, C.sub.1-C.sub.2-halogenoalkoxy,
nitro or cyano, or represents the groups 15
[0058] or cyano, where
[0059] l particularly preferably represents 0 to 1,
[0060] R.sup.1 particularly preferably represents hydrogen (but not
for the radicals --CO.sub.2R.sup.1 and --SO.sub.2R.sup.1),
represents in each case optionally fluorine- and/or
chlorine-substituted C.sub.1-C.sub.6-alkyl,
C.sub.2-C.sub.6-alkenyl, C.sub.3-C.sub.4-alkinyl, represents
optionally fluorine-, chlorine-, C.sub.1-C.sub.2-alkyl-,
C.sub.1-C.sub.2-alkoxy-substituted C.sub.3-C.sub.6-cycloalkyl or
represents phenyl or benzyl, 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-halogenoalkyl, C.sub.1-C.sub.2-halogenoalkoxy,
cyano or nitro,
[0061] R.sup.2 particularly preferably represents hydrogen,
represents in each case optionally fluorine- and/or
chlorine-substituted C.sub.1-C.sub.4-alkyl,
C.sub.3-C.sub.4-alkenyl, C.sub.3-C.sub.4-alkinyl,
C.sub.1-C.sub.4-alkoxy, C.sub.3-C.sub.4-alkenyloxy or represents
phenyl, benzyl or benzyloxy, 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-halogenoalkyl, C.sub.1-C.sub.2-halogenoalkoxy,
cyano or nitro, or
[0062] R.sup.1,R.sup.2 together with the nitrogen atom to which
they are attached particularly preferably furthermore represent an
optionally C.sub.1-C.sub.2-alkyl-substituted five- or six-membered
cycle in which optionally one methylene group may be replaced by
oxygen,
[0063] R.sup.3 particularly preferably represents hydrogen,
represents C.sub.1-C.sub.4-alkyl or represents phenyl or benzyl,
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,
trifluoromethyl, difluoromethoxy, trifluoromethoxy, cyano or
nitro,
[0064] R.sup.4,R.sup.5,
[0065] R.sup.6 each particularly preferably represent hydrogen,
methyl or ethyl,
[0066] R.sup.7 particularly preferably represents in each case
optionally fluorine- and/or chlorine-substituted
C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.3-C.sub.6-alkinyl, C.sub.1-C.sub.6-alkoxy,
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, in each case
optionally fluorine- and/or chlorine-, C.sub.1-C.sub.2-alkyl-,
C.sub.1-C.sub.2-alkoxy-substituted C.sub.3-C.sub.6-cycloalkyl or
C.sub.3-C.sub.6-cycloalkoxy in which optionally one methylene group
may be replaced by oxygen, represents phenyl, phenoxy, benzyloxy,
thienyl, furanyl, pyridyl, pyrimidyl, thiazolyl, pyrazolyl 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, trifluoromethyl,
difluoromethoxy, trifluoromethoxy, cyano or nitro, or, in the case
of the radicals a) and c) mentioned under Ar, also represents a
group 16
[0067] or, for the radical g), also represents hydroxyl,
[0068] R.sup.8 particularly preferably represents hydrogen,
[0069] R.sup.9 particularly preferably represents hydrogen, in each
case optionally fluorine- and/or chlorine-substituted
C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-alkenyl,
C.sub.3-C.sub.6-alkinyl, C.sub.1-C.sub.6-alkoxy,
C.sub.3-C.sub.6-cycloalkyl, in which optionally one methylene group
may be replaced by oxygen, 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, trifluoromethyl,
difluoromethoxy, trifluoromethoxy, cyano or nitro,
[0070] R.sup.10 particularly preferably represents hydrogen or
C.sub.1-C.sub.4-alkyl,
[0071] R.sup.9, R.sup.10 together with the nitrogen atom to which
they are attached particularly preferably furthermore represent an
optionally C.sub.1-C.sub.2-alkyl-substituted five- to six-membered
cycle in which optionally one methylene group may be replaced by
oxygen,
[0072] m particularly preferably represents 1 to 3,
[0073] n depending on m, particularly preferably represents 0 to
2.
[0074] K very particularly preferably represents oxygen or
sulphur.
[0075] Ar very particularly preferably represents Ar.sup.1, where
Ar.sup.1 represents phenyl, thienyl, pyrimidyl, furanyl or pyridyl,
each of which is optionally mono- to trisubstituted by fluorine,
chlorine, bromine, methyl, ethyl, propyl, i-propyl, s-, n-, i- or
t-butyl, methoxy, ethoxy, propoxy, i-propoxy, s-, n-, i- or
t-butoxy, allyloxy, methallyloxy, 2-butenyloxy, propargyloxy,
2-butinyloxy, methylthio, ethylthio, methylsulphinyl,
ethylsulphinyl, methylsulphonyl, ethylsulphonyl, trifluoromethyl,
difluoromethoxy, trifluoromethoxy, methylenedioxy,
difluoromethylenedioxy, tetrafluoroethylenedioxy,
difluoromethylthio, trifluoromethylthio, trifluoromethylsulphinyl,
trifluoromethylsulphonyl, hydroxyl, mercapto, nitro, cyano, amino
or by one of the following groups 17
[0076] or represents Ar.sup.2, where Ar.sup.2 represents Ar.sup.1
which is additionally substituted by phenyl, pyridyl, thienyl,
tetrazolyl, triazolyl or phenoxy, where these substituents for
their part are optionally mono- to disubstituted by fluorine,
chlorine, bromine, methyl, ethyl, n- or i-propyl, s-, n-, i- or
t-butyl, methoxy, ethoxy, i-propoxy, s-, n- or t-butoxy,
trifluoromethyl, trifluoromethoxy, nitro or cyano, and
[0077] L very particularly preferably represents oxygen or
sulphur.
[0078] X very particularly preferably represents --CN,
--CO--NH.sub.2, 18
[0079] Y very particularly preferably represents methyl, phenyl
which is optionally mono- to trisubstituted by fluorine, chlorine,
bromine, methyl, methoxy, trifluoromethyl or trifluoromethoxy, or
represents the group --CO.sub.2R.sup.1,
[0080] Two adjacent Y.sub.n may furthermore very particularly
preferably represent a six-membered unsaturated cycle which may
optionally be monosubstituted by fluorine, chlorine, bromine,
methyl, methoxy, trifluoromethyl, trifluoromethoxy, cyano or
nitro,
[0081] Z very particularly preferably represents hydrogen, methyl,
ethyl, allyl, propargyl, cyclopropyl, cyclopentyl, cyclohexyl,
cyclopropylmethyl, cyclopentylmethyl, cyclohexylmethyl,
methoxymethyl, ethoxymethyl, represents phenyl, benzyl,
pyridylmethyl, thiazolylmethyl, each of which is optionally mono-
to disubstituted by fluorine, chlorine, bromine, methyl, methoxy,
trifluoromethyl or trifluoromethoxy, cyano or nitro, or represents
the groups 19
[0082] or cyano, where
[0083] R.sup.1 very particularly preferably represents hydrogen
(but not for the radicals --COCO.sub.2R.sup.1 and
--SO.sub.2R.sup.1), methyl, ethyl, propyl, isopropyl, n-, s-, i- or
t-butyl, allyl, propargyl, cyclopropyl, cyclopentyl, cyclohexyl,
represents phenyl or benzyl, each of which is optionally mono- to
disubstituted by fluorine, chlorine, bromine, methyl, methoxy,
trifluoromethyl, trifluoromethoxy, cyano or nitro,
[0084] R.sup.2 very particularly preferably represents hydrogen,
methyl, ethyl, propyl, isopropyl, allyl, propargyl, methoxy,
ethoxy, allyloxy or represents benzyloxy which is optionally mono-
to disubstituted by fluorine, chlorine, bromine, methyl, methoxy,
trifluoromethyl, trifluoromethoxy, cyano or nitro, or
[0085] R.sup.1, R.sup.2 together with the nitrogen atom to which
they are attached very particularly preferably furthermore
represent a pyrrolidine, thiazine, piperidine or morpholine
radical,
[0086] R.sup.3, R.sup.5 each very particularly preferably represent
hydrogen, methyl or ethyl,
[0087] R.sup.7 very particularly preferably represents methyl,
ethyl, propyl, isopropyl, n-, s-, i- or t-butyl, vinyl,
trifluoromethyl, methoxy, ethoxy, propoxy, isopropoxy, n-, s-, i-
or t-butyloxy, cyclopropyl, cyclopentyl, cyclohexyl,
cyclopentyloxy, cyclohexyloxy, represents phenyl, pyridyl or
benzyl, each of which is optionally mono- to disubstituted by
fluorine, chlorine, bromine, methyl, n-, s-, i- or t-butyl,
methoxy, trifluoromethyl, trifluoromethoxy, cyano or nitro, or, in
the case of the radicals a) and c) mentioned under Ar, also
represents a group 20
[0088] or, for the radical g), also represents hydroxyl,
[0089] R.sup.9 very particularly preferably represents hydrogen,
methyl, ethyl, propyl, isopropyl, n-, s-, i- or t-butyl,
cyclopropyl, cyclopentyl, cyclohexyl, represents phenyl which is
optionally mono- to disubstituted by fluorine, chlorine, bromine,
methyl, methoxy, trifluoromethyl, trifluoromethoxy, cyano or
nitro,
[0090] R.sup.10 very particularly preferably represents hydrogen,
methyl or ethyl,
[0091] R.sup.9, R.sup.10 together with the nitrogen atom to which
they are attached very particularly preferably represent a
pyrrolidine, piperidine or morpholine radical.
[0092] m very particularly preferably represents 1 to 3.
[0093] n depending on m, very particularly preferably represents 0
to 1.
[0094] K most preferably represents oxygen or sulphur.
[0095] Ar most preferably represents Ar.sup.1, where Ar.sup.1
represents phenyl, thienyl, pyrimidyl or pyridyl, each of which is
optionally mono- to trisubstituted by fluorine, chlorine, bromine,
methyl, ethyl, propyl, isopropyl, n-, s-, i- or t-butyl, methoxy,
ethoxy, propoxy, isopropoxy, n-, s-, i- or t-butoxy, allyloxy,
methallyloxy, 2-butenyloxy, propargyloxy, 2-butinyloxy, methylthio,
ethylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl,
ethylsulphonyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy,
methylenedioxy, difluoromethylenedioxy, tetrafluoroethylenedioxy,
difluoromethylthio, trifluoromethylthio, trifluoromethylsulphinyl,
trifluoromethylsulphonyl, hydroxyl, nitro, mercapto, cyano,
amino,
[0096] or represents Ar.sup.2, where Ar.sup.2 represents Ar.sup.1
which is additionally substituted by phenyl or phenoxy, where these
substituents for their part are optionally mono- to disubstituted
by fluorine, chlorine, bromine, methyl, ethyl, isopropyl, n-, s-,
i- or t-butyl, methoxy, ethoxy, isopropoxy, n-, s-, i- or t-butoxy,
trifluoromethyl, trifluoromethoxy, nitro or cyano.
[0097] X most preferably represents CN.
[0098] Z most preferably represents hydrogen and methyl.
[0099] m most preferably represents 1 to 3.
[0100] n most preferably represents 0.
[0101] All of the compounds of the formula (I) listed above can be
present both as cis- and as trans-isomers. To simplify the
presentation, in each case only one isomer was shown in the
description of the compounds by formulae. However, the invention
also refers to the respective other isomer.
[0102] The abovementioned general or preferred radical definitions
apply both to the end products of the formula (I) and,
correspondingly, to the starting materials and intermediates
required in each case for the preparation. These radical
definitions can be combined with one another at will, i.e.
including combinations between the given preferred ranges.
[0103] Preference according to the invention is given to the
compounds of the formula (I) which contain a combination of the
meanings listed above as being preferred (preferable).
[0104] Particular preference according to the invention is given to
the compounds of the formula (I) which contain a combination of the
meanings listed above as being particularly preferred.
[0105] Very particular preference according to the invention is
given to the compounds of the formula (I) containing a combination
of the meanings listed above as being very particularly
preferred.
[0106] Most preference according to the invention is given to the
compounds of the formula (I) which contain a combination of the
meanings listed above as being most preferred.
[0107] Saturated or unsaturated hydrocarbon radicals, such as alkyl
or alkenyl, can in each case be straight-chain or branched, as far
as this is possible, including in combination with heteroatoms,
such as, for example, in alkoxy.
[0108] Unless stated otherwise, optionally substituted radicals can
be mono- or polysubstituted, and in the case of polysubstitutions,
the substituents can be identical or different.
[0109] Examples of the compounds of the formula (I) according to
the invention are listed in the groups below: 21
[0110] (O).sub.p (p=1 to 3) has here, for example, the meanings
given in the list below: fluorine, chlorine, bromine, methyl,
ethyl, propyl, isopropyl, n-, s-, i- or t-butyl, methoxy, ethoxy,
propoxy, isopropoxy, n-, s-, i- or t-butoxy, allyloxy,
methallyloxy, 2-butenyloxy, propargyloxy, 2-butinyloxy, methylthio,
ethylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl,
ethylsulphonyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy,
methylenedioxy, difluoromethylenedioxy, tetrafluoroethylenedioxy,
difluoromethylthio, trifluoromethylthio, trifluoromethylsulphinyl,
trifluoromethylsulphonyl, hydroxyl, mercapto, nitro, cyano, amino.
22
[0111] Q and p have here, for example, the meanings given above in
Group 1. 23
[0112] Q and p have here, for example, the meanings given above in
Group 1 (but p=0 to 2). 24
[0113] Q and p have here, for example, the meanings given above in
Group 1 (but p=0 to 2). 25
[0114] Q and p have here, for example, the meanings given above in
Group 1 (but p=0 to 2). 26
[0115] Q and p have here, for example, the meanings given above in
Group 1 (but p=0 to 2). 27
[0116] Q and p have here, for example, the meanings given above in
Group 1 (but p=0 to 2). 28
[0117] Q and p have here, for example, the meanings given above in
Group 1 (but p=0 to 2). 29
[0118] Q and p have here, for example, the meanings given above in
Group 1 (but p=0 to 2). 30
[0119] Q and p have here, for example, the meanings given above in
Group 1 (but p=0 to 2). 31
[0120] Q and p have here, for example, the meanings given above in
Group 1 (but p=0 to 2). 32
[0121] Q and p have here, for example, the meanings given above in
Group 1 (but p=0 to 2).
[0122] It has been found that the novel compounds of the formula
(I) are obtained by the process described below:
[0123] (A) Compounds of the formula (I) 33
[0124] in which
[0125] Ar, X, Y, m, n are each as defined above and
[0126] K represents oxygen and
[0127] Z represents hydrogen
[0128] are obtained when
[0129] compounds of the formula (II) 34
[0130] in which
[0131] Ar and X are each as defined above,
[0132] are reacted with compounds of the formula (III) 35
[0133] in which
[0134] Y, m, n are each as defined above and
[0135] W represents O or S(O).sub.g, where g represents 0 or 2,
and
[0136] R.sup.11 represents alkyl, in particular represents
C.sub.1-C.sub.6-alky, or benzyl,
[0137] if appropriate in the presence of a diluent and if
appropriate in the presence of a base or an acid and/or a metal
compound of the formula (IIIa)
Me(V).sub.2 (IIa)
[0138] in which
[0139] Me represents a divalent transition metal atom, in
particular nickel, and
[0140] V represents a chelate ligand, in particular a bidentate
chelate ligand, such as, for example, acetylacetonate (R. G.
Glushkov et al., Khim.-Farm. Zh. 24, (7), (1990), 24-27; M. V.
Mezentseva et al., Khim.-Farm. Zh. 25,(12), (1991), 19-23; G.
Dannhardt, A. Bauer, Pharmazie 51,(1996), 805-810).
[0141] (B) Moreoveer, it has been found that compounds of the
formula (I) 36
[0142] in which
[0143] Ar, Y, X, m, n are each as defined above and
[0144] K represents oxygen and
[0145] Z represents hydrogen,
[0146] are obtained when compounds of the formula (IV) 37
[0147] in which
[0148] Ar and X are each as defined above and
[0149] Hal represents halogen, in particular chlorine or
bromine,
[0150] are reacted with compounds of the formula (V) 38
[0151] in which
[0152] Y, m and n are each as defined above,
[0153] if appropriate in the presence of a diluent, to give
compounds of the formula (VI) 39
[0154] in which
[0155] Ar, X, Y, m and n are each as defined above,
[0156] which are reacted further, if appropriate in the presence of
a base and if appropriate in the presence of a trivalent phosphorus
compound (for example triphenylphosphine, triethyl phosphite) with
elimination of sulphur and hydrogen halide, to give compounds of
the formula (I),
[0157] in which
[0158] Ar, X, Y, m and n are each as defined above and
[0159] Z represents hydrogen
[0160] (see A. Eschenmoser et al., Helv. Chim. Acta 54, (1971),
710-734; V. Issartel et al., C.R. Acad. Sci., Ser. II, Mec., Phys.,
Chim., Astron. 321, (12), (1995), 521-524).
[0161] (C) Furthermore, it has been found that compounds of the
formula (I) 40
[0162] in which
[0163] Ar, Z, X, Y, m and n each have one of the meanings given
above and
[0164] K represents oxygen but
[0165] Z does not represent hydrogen, are obtained when
[0166] compounds of the formula (VII) 41
[0167] in which
[0168] Y, Z, m and n
[0169] each have one of the meanings given above
[0170] and Z does not represent hydrogen,
[0171] are reacted with halogenating agents, such as, for example,
phosgene, diphosgene and triphosgene, if appropriate in the
presence of a diluent, to give compounds of the formula (VIII)
42
[0172] in which
[0173] Y, Z, m and n each have one of the meanings given above
[0174] and Z does not represent hydrogen and
[0175] Hal represents halogen, in particular chlorine or
bromine,
[0176] which are then reacted with compounds of the formula (II)
43
[0177] in which
[0178] Ar, X are each as defined above,
[0179] if appropriate in the presence of a diluent and if
appropriate in the presence of an acid acceptor (see G. Dannhardt,
A. Bauer, Pharmazie 51, (1996), 805-810).
[0180] (D) Furthermore, it has been found that compounds of the
formula (I) 44
[0181] in which
[0182] Ar, Z, X, Y, m and n each have one of the meanings given
above and
[0183] K represents oxygen, but
[0184] Z does not represent hydrogen,
[0185] are obtained when
[0186] compounds of the formula (I-a) 45
[0187] in which
[0188] Ar, X, Y, m and n are each as defined above,
[0189] are reacted with alkylating agents, acylating agents,
sulphonylating agents or condensing agents of the formula (IX)
Z-G (IX),
[0190] in which
[0191] G represents a leaving group, such as halogen, in particular
iodine, bromine, chlorine, sulphonate, such as, for example,
mesylate, triflate or toluenesulphonate, or alkoxy,
[0192] if appropriate in the presence of a solvent and if
appropriate in the presence of a base.
[0193] (E) Moreover, it has been found that compounds of the
formula (I) 46
[0194] in which
[0195] Ar.sup.2, X, Y, Z, m and n are each as defined above and
[0196] K represents oxygen,
[0197] are obtained when compounds of the formula (II) 47
[0198] in which
[0199] Ar.sup.1, X, Y, Z, m and n are each as defined above and
[0200] Hal represents halogen, in particular bromine,
[0201] are reacted with boronic acids of the formula (X)
Ar.sup.1--B(OH).sub.2 (X),
[0202] in which
[0203] Ar.sup.2' represents the substituents which have been
mentioned above under Ar.sup.2 as additional substituents for
Ar.sup.1,
[0204] in the presence of a solvent, if appropriate in the presence
of a base and a noble metal complex, preferably a palladium
complex.
[0205] (F) Furthermore, it has been found that compounds of the
formula (I) 48
[0206] in which
[0207] Ar, X, Y, Z, m and n are each as defined above and
[0208] K represents sulphur,
[0209] are obtained when compounds of the formula (I) 49
[0210] in which
[0211] Ar, X, Y, Z, m and n are each as defined above and
[0212] K represents oxygen,
[0213] are reacted in the presence of a sulphurizing agent, such
as, for example, phosphorus pentasulphide or
2,4-bis(4-methoxyphenyl)-1,2,3,4-dit- hiaphosphetane-2,4-disulphide
(Lawesson's reagent), in the presence of a solvent.
[0214] Using, according to process A, for example
4-methyl-benzoylacetonit- rile and 2-methoxy-1-pyrroline as
starting materials, the course of the reaction can be represented
by the following reaction scheme: 50
[0215] Using, according to process B, for example
2-bromo-2-(3-chlorobenzo- yl)acetonitrile and pyrrolidine-2-thione
as starting materials, the course of the reaction can be
represented by the following reaction scheme: 51
[0216] Using, according to process C, for example
3,4-dichloro-benzoyl-ace- tonitrile and N-methyl-pyrrolidone as
starting materials, the course of the reaction can be represented
by the following reaction scheme: 52
[0217] Using, according to process D, for example
3-oxo-2-pyrrolidin-2-yli-
dene-3-(4-trifluoromethoxy-phenyl)-propionitrile and
2-chloro-5-chloromethyl-pyridine as starting materials, the course
of the reaction can be represented by the following reaction
scheme: 53
[0218] Using, according to process D, for example
3-oxo-2-pyrrolidin-2-yli-
dene-3-(4-trifluoromethyl-phenyl)-propionitrile and 4-chlorobenzoyl
chloride as starting materials, the course of the reaction can be
represented by the following reaction scheme: 54
[0219] Using, according to process E, for example
3-oxo-2-pyridin-2-yliden- e-3-(4-bromo-phenyl)-propionitrile and
4-chloro-phenylboronic acid as starting materials, the course of
the reaction can be represented by the following reaction scheme:
55
[0220] Using, according to process F, for example
3-oxo-2-pyrrolidine-3-(4- -chlorophenyl)propionitrile as starting
material and Lawesson'sreagent, the course of the reaction can be
represented by the following reaction scheme: 56
[0221] Some of the compounds of the formula (II) 57
[0222] in which
[0223] Ar, X are each as defined above,
[0224] required as starting materials in the process (A) are novel
and can be prepared by processes known in principle from the
literature (Organikum, 16.sup.th revised edition, pp. 415, 417, VEB
Deutscher Verlag der Wissenschaften, Berlin 1986).
[0225] From among the compounds of the formula (II), the novel
compounds of the formula (II-1-b), 58
[0226] where
[0227] T is as defined in the table below:
1 Comp. No. T M.p..degree. C. II-1-b-1 3-Cl, 4-F 78 II-1-b-2 4-Cl,
3-F 87 II-1-b-3 3,5-(CF.sub.3).sub.2 91 II-1-b-4 2,4-Cl.sub.2, 5-F
106 II-1-b-5 3,5-Cl.sub.2, 4-F 138-140 II-1-b-6 4-Cl, 2-F 90-94
II-1-b-7 3-CF.sub.3, 5-CH.sub.3 92 II-1-b-8 3-Cl, 4,5-F.sub.2 84-88
II-1-b-9 4-CN, 2,5-F.sub.2 107-108 II-1-b-10 2,3-F.sub.2 74
II-1-b-11 3-F, 4-CF.sub.3 92 II-1-b-12 3,4-O--CF.sub.2--O 70-73
II-1-b-13 3-NO.sub.2, 5-CF.sub.3 II-1-b-14 4-Cl, 2,5-F.sub.2 116
II-1-b-15 3,4,5-(OC.sub.2H.sub.5)- .sub.3 122 II-1-b-16 4-Br, 2-F
118 II-1-b-17 2,6-Cl.sub.2, 4-CF.sub.3 123 II-1-b-18 2-F,
4-NO.sub.2 168 II-1-b-19 2,4-Cl.sub.2, 5-NO.sub.2 100 II-1-b-20
4-Cl, 2-F, 5-NO.sub.2 118 II-1-b-21 2,4-F.sub.2, 5-NO.sub.2 128
II-1-b-22 4-Br, 2-F, 5-NO.sub.2 141 II-1-b-23 2-F, 4-CF.sub.3 62
II-1-b-24 4-OCF.sub.3, 3-NO.sub.2 95 II-1-b-25 4-Cl, 2-NO.sub.2 130
II-1-b-26 2-F, 3-CF.sub.3 67-69 II-1-b-27 2-Cl, 6-F 46-48 II-1-b-28
2-Cl, 3-CF.sub.3 90-93 II-1-b-29 3,4-O--(CF.sub.2).sub.2--O-- 206
II-1-b-30 2-Cl, 4-SCH.sub.3 110 II-1-b-31 2-Cl, 4-SO.sub.2CH.sub.3
202
[0228] and the compound of the formula (II-2-b) 59
[0229] where T is as defined in the table below:
2 Comp. No. T M.p..degree. C. II-2-b-1 2,6-Cl.sub.2 >220
II-2-b-2 2,6-Cl.sub.2, 4-CH.sub.3 95 II-2-b-3 6-Cl 122
[0230] and the compound of the formula (II-3-b) 60
[0231] where T is as defined in the table below:
3 Comp. No. T M.p..degree. C. II-3-b-1 2-CF.sub.3,
3-(4-Cl'--C.sub.6H.sub.4) oil II-3-b-2 2-CF.sub.3,
3-(2,4-Cl.sub.2'--C.sub.6H.sub.3) oil
[0232] and the compound No. II-4-b-1 61
[0233] and the compound N. II-5-b-1 62
[0234] are particularly suitable for preparing novel pesticidal, in
particular acaricidal, herbicidal and insecticidal end
products.
[0235] The compounds of the formula (II) are obtained, for example,
by hydrolysing and then decarboxylating compounds of the formula
(XI) 63
[0236] in which
[0237] Ar is as defined above,
[0238] R.sup.12 represents alkyl, in particular
C.sub.1-C.sub.6-alkyl, or benzyl, which may optionally be
substituted,
[0239] in the presence of an acid (for example an inorganic acid,
such as hydrogen chloride) or a base (for example an alkali metal
hydroxide, such as sodium hydroxide or potassium hydroxide) and, if
appropriate, in the presence of a diluent (for example an aqueous
alcohol, such as methanol or ethanol) at temperatures between
0.degree. C. and 200.degree. C., preferably between 20.degree. C.
and 150.degree. C., where the removal of the radical R.sup.12 may,
if desired, also be effected hydrolytically by known processes
(Bowman, Fordham, J. Chem. Soc. 1951, 2758) using molecular
hydrogen at pressures between 1 and 100 bar, if appropriate in the
presence of a solvent, such as, for example, methanol, ethanol or
ethyl acetate, at temperatures between -20 and 100.degree. C.,
preferably at room temperature, in the presence of a transition
metal, such as, for example, palladium, nickel, rhodium or
platinum, which is, if appropriate, immobilized on a carrier, such
as, for example, activated carbon or barium sulphate.
[0240] The compounds of the formula (XI) can be prepared by known
processes (Organikum, 16.sup.th revised edition, p. 480, VEB
Deutscher Verlag der Wissenschaften, Berlin 1986).
[0241] The compounds of the formula (XI) are obtained, for example,
by reacting compounds of the formula (XII) 64
[0242] in which
[0243] Ar is as defined above,
[0244] with cyanoacetates of the formula (XIII) 65
[0245] in which
[0246] R.sup.12 represents alkyl, in particular
C.sub.1-C.sub.6-alkyl,
[0247] in the presence of a base (for example a metal alkoxide,
such as sodium methoxide or sodium ethoxide) and, if appropriate,
in the presence of a diluent (for example ether or the alcohol
derived from the alkoxide), at temperatures from 0.degree. C. to
150.degree. C., preferably between 20.degree. C. and 120.degree.
C.
[0248] Some of the compounds of the formula (XII) are novel and can
be prepared by processes known in principle (for example Organikum,
16.sup.th revised edition, p. 423, VEB Deutscher Verlag der
Wissenschaften, Berlin 1986).
[0249] The compounds of the formula (XI) are obtained, for example,
by reacting compounds of the formula (XIV) 66
[0250] in which
[0251] Ar is as defined above,
[0252] with halogenating agents (for example thionyl chloride,
phosgene, phosphorus trichloride), if appropriate in the presence
of a diluent (for example optionally chlorinated aliphatic or
aromatic hydrocarbons, such as toluene or methylene chloride), at
temperatures of from 0.degree. C. to 150.degree. C., preferably
between 20.degree. C. and 100.degree. C.
[0253] Cyanoacetates of the formula (XIII) are known compounds of
organic chemistry.
[0254] The compounds of the formula (III) 67
[0255] in which
[0256] Y, R.sup.11, m and n are each as defined above and
[0257] W represents oxygen,
[0258] also required as starting materials for the process (A) can
be prepared by known processes (Pendrak et al., J. Org. Chem. 60,
(1995), 2912-2915).
[0259] The compounds of the formula (III) are obtained, for
example, by reacting compounds of the formula (VII) 68
[0260] in which
[0261] Y, m and n are each as defined above and
[0262] Z represents hydrogen,
[0263] with alkylating agents (for example dimethyl sulphate,
triethyloxonium tetrafluoroborate (Meerwein salt)), at temperatures
of from -20.degree. C. to 150.degree. C., preferably of from
0.degree. C. to 100.degree. C., if appropriate in the presence of a
diluent.
[0264] The compounds of the formula (III) 69
[0265] in which
[0266] Y, R.sup.11, m, n are each as defined above and
[0267] W represents sulphur,
[0268] required as starting materials for the process A are
furthermore obtained when compounds of the formula (VII) 70
[0269] in which
[0270] Y, m and n are each as defined above and
[0271] Z represents hydrogen
[0272] are initially converted with a sulphurizing reagent, for
example Lawesson's reagent, into the thioamide of the formula (V)
71
[0273] in which
[0274] Y, m and n are each as defined above and Z represents
hydrogen
[0275] in the presence of a solvent, and subsequently reacted with
an alkylating agent of the formula (XV),
R.sup.11-Hal (XV)
[0276] in which
[0277] R.sup.11 is as defined above and
[0278] Hal represents halogen, in particular iodine and
bromine,
[0279] if appropriate in the presence of a base and if appropriate
in the presence of a solvent.
[0280] The process (A) is characterized in that compounds of the
formula (II) in which
[0281] Ar, X are each as defined above,
[0282] and compounds of the formula (III)
[0283] in which
[0284] R.sup.11, W, Y, m, n are each as defined above,
[0285] are reacted in the presence of a diluent and, if
appropriate, in the presence of a base.
[0286] Suitable diluents for the process (A) are all organic
solvents which are inert towards the reactants. Preference is given
to using optionally chlorinated aliphatic or aromatic hydrocarbons,
such as toluene, xylene or methylene chloride, and furthermore
polar solvents, such as dimethyl sulphoxide, dimethylformamide or
N-methylpyrrolidone.
[0287] Suitable bases for carrying out the process (A) are all
customary acid acceptors which do not hydrolyse the reactants.
[0288] Preference is given to using tertiary amines, such as
triethylamine, pyridine or N,N-dimethylaniline.
[0289] Suitable acids for carrying out process (A) are all acids
which do not hydrolyse the reactants. Preference is given to using
organic acids, such as p-toluenesulphonic acid and trifluoroacetic
acid.
[0290] When carrying out the process (A), the reaction temperature
can be varied within a relatively wide range. Advantageously, the
process is carried out at temperatures between -20.degree. C. and
160.degree. C., preferably between 0.degree. C. and 120.degree.
C.
[0291] The process (A) is preferably carried out under atmospheric
pressure.
[0292] When carrying out the process (A), the reaction components
of the formula (III) are employed in an equimolar amount or in a
relatively large excess (up to 5 mol), preferably in 1.5 to 2 times
the molar amount, based on the reaction component of the formula
(II).
[0293] The base which is used, if appropriate, is preferably
employed in an equimolar amount to the reaction component of the
formula (II). The acid which is used, if appropriate, is preferably
employed in catalytic amounts.
[0294] The process (B) is characterized in that compounds of the
formula (IV) are in each case reacted with thioamides of the
formula (V), if appropriate in the presence of a diluent and if
appropriate in the presence of an acid binder.
[0295] The starting materials of the formula (IV) can be prepared
by known processes (Gakhar H. K. et al., J. Indian Chem. Soc., 43,
(1971), 953 or Corsaro A., Heterocycles 23, (1985), 2645). The
compounds of the formula (V) can be prepared from the corresponding
keto compound using thionylating agents, in particular Lawesson's
reagent, in inert solvents, such as, for example, toluene (see
Preparation Example 9). With the exception of
5-phenyl-pyrrolidine-2-thione (see Lettau et al. PHARAT, Pharmazie
48 (1993) 410) and 5-(3,4-dimethoxy-phenyl)-pyrrolidine-2-thion- e,
the substituted 5-phenyl-pyrrolidone-2-thiones and
6-phenyl-piperidine-2-thiones of the formula (V) are novel.
[0296] Suitable diluents for the process (B) according to the
invention are all solvents which are inert towards the compounds of
the formula (IV). Preference is given to using hydrocarbons, such
as benzine, benzene, toluene, xylene and tetralin, furthermore
halogenated hydrocarbons, such as methylene chloride, chloroform,
carbon tetrachloride, chlorobenzene and o-dichlorobenzene, moreover
ketones, such as acetone and methyl isopropyl ketone, furthermore
ethers, such as diethyl ether, tetra-hydrofuran and dioxane,
additionally carboxylic esters, such as ethyl acetate, and also
strongly polar solvents, such as dimethylformamide,
N-methylpyrrolidone, dimethylsulphoxide and sulpholane.
[0297] Suitable acid binders for the reaction according to process
(B) 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, polymeric bases, such as
diisopropylaminopolystyrene, 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.
[0298] Suitable phorphorus reagents for the process (B) according
to the invention are alkyl phosphites, such as triethyl phosphite,
tributyl phosphite, or triphenylphosphines, such as
triphenylphosphine.
[0299] When carrying out the process (B) according to the
invention, the reaction temperature can be varied within a
relatively wide range. In general, the process is carried out at
temperatures between 0.degree. C. and 200.degree. C., preferably
between -20.degree. C. and 150.degree. C.
[0300] When carrying out the process (B) according to the
invention, the starting materials of the formula (IV) and the
thioamide of the formula (V) are generally in each case employed in
approximately equivalent amounts. However, it is also possible to
use a relatively large excess of one or the other component.
Work-up is carried out by customary methods.
[0301] The process (C) is characterized in that compounds of the
formula (VII) are reacted with halogenating agents, such as, for
example, phosgene, diphosgene, triphosgene, if appropriate in the
presence of a diluent, to give compounds of the formula (VIII)
which are then reacted with compounds of the formula (I), if
appropriate in the presence of an acid binder and if appropriate in
the presence of a diluent. Some of the starting materials of the
formula (VII), such as, for example, N-methyl-pyrrolidone, are
commercially available, or they can be prepared by known
processes.
[0302] Suitable acid binders for the reaction according to the
process (C) 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, polymeric bases, such as, for example,
diisopropylaminopolystyrene, 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.
[0303] Suitable diluents for the process (C) according to the
invention are all solvents which are inert towards the halogenating
agents. Preference is given to using hydrocarbons, such as benzine,
benzene, toluene, xylene and tetralin, furthermore halogenated
hydrocarbons, such as methylene chloride, chloroform, carbon
tetrachloride, chlorobenzene and o-dichlorobenzene, moreover
ketones, such as acetone and methyl isopropyl ketone, furthermore
ethers, such as diethyl ether, tetrahydrofuran and dioxane,
additionally carboxylic esters, such as ethyl acetate, moreover
nitriles, such as acetonitrile, and also strongly polar solvents,
such as dimethyl sulphoxide and sulpholane.
[0304] When carrying out the process (C) according to the
invention, the reaction temperature can be varied within a
relatively wide range. In general, the process is carried out at
temperatures between -20.degree. C. and 100.degree. C., preferably
between 0.degree. C. and 80.degree. C.
[0305] The process (C) according to the invention is generally
carried out under atmospheric pressure.
[0306] When carrying out the process (C) according to the
invention, the starting materials of the formula (VI) and the
appropriate halogenating agent are generally in each case employed
in approximately equivalent amounts. However, it is also possible
to use a relatively large excess (up to 3 mol) of one or the other
component. Work-up is carried out by customary methods. In general,
precipitated salts are removed and the reaction mixture that
remains is concentrated by stripping off the diluent.
[0307] The process (I) is characterized in that compounds of the
formula (I) in which Ar, X, Y, m and n are each as defined above
and Z represents hydrogen are in each case reacted with alkylating
agents, acylating agents, sulphonylating agents or condensing
agents of the formula (IX), if appropriate in the presence of a
diluent and if appropriate in the presence of an acid binder.
[0308] The alkylating agents, acylating agents, sulphonylating
agents or condensing agents of the formula (IX) to be used are
known synthesis chemicals of organic chemistry.
[0309] Suitable diluents for the process (D)) according to the
invention aree all solvents which are inert towards the
abovementioned reagents. Preference is given to using hydrocarbons,
such as benzine, benzene, toluene, xylene and tetralin, furthermore
halogenated hydrocarbons, such as methylene chloride, chloroform,
carbon tetrachloride, chlorobenzene and o-dichlorobenzene, moreover
ketones, such as acetone and methyl isopropyl ketone, furthermore
ethers, such as diethyl ether, tetrahydrofuran and dioxane,
additionally carboxylic esters, such as ethyl acetate, and also
strongly polar solvents such as, for example, dimethyl sulphoxide,
dimethylformamide, N-methylpyrrolidone and sulpholane. The
hydrolytic stability of the acylating agents and sulphonylating
agents permitting, the reaction can also be carried out in the
presence of water.
[0310] Suitable acid binders for the reaction according to the
process (D) 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, and
furthermore alkali metal hydrides, such as sodium hydride,
potassium hydride, or alkali metal alkoxides, such as potassium
tert-butoxide.
[0311] When carrying out the process (D) according to the
invention, the reaction temperatures can be varied within a
relatively wide range. In general, the process is carried out at
temperatures between -70.degree. C. and +150.degree. C., preferably
between -20.degree. C. and 100.degree. C.
[0312] When carrying out the process (D) according to the
invention, the above-mentioned starting materials of the formula
(I) and the abovementioned reagents of the formula (IX) are
generally in each case employed in approximately equivalent
amounts. However, it is also possible to use a relatively large
excess (up to 5 mol) of the abovementioned reagents. Work-up is
carried out by customary methods.
[0313] Preferred catalysts for carrying out the process (E)
according to the invention are palladium(0) complexes. Preference
is given, for example, to
tetrakis(triphenylphosphine)palladium.
[0314] Some of the arylboronic acids required for carrying out the
process (E) are commercially available, such as, for example,
4-chloro-phenylboronic acid, or they can be prepared by known
processes.
[0315] Suitable acid acceptors for carrying out the process (E)
according to the invention are inorganic or organic bases. These
preferably include alkaline earth metal or alkali metal hydroxides,
acetates, carbonates or bicarbonates, such as, for example, sodium
hydroxide, potassium hydroxide, barium hydroxide or ammonium
hydroxide, sodium acetate, potassium acetate, calcium acetate or
ammonium acetate, sodium carbonate, potassium carbonate or ammonium
carbonate, sodium bicarbonate or potassium bicarbonate, alkali
metal fluorides, such as, for example, caesium fluoride, and also
tertiary amines, such as trimethylamine, triethylamine,
tributylamine, N,N-dimethylaniline, N,N-dimethylbenzylamine,
pyridine, N-methylpiperidine, N-methylmorpholine,
N,N-dimethylaminopyridine, diazabicyclooctane (DABCO),
diazabicycloundecene (DBU), diazabicyclononene (DBN).
[0316] Suitable diluents for carrying out the process (E) according
to the invention are water, organic solvents and any mixtures of
these. Examples which may be mentioned are: aliphatic, alicyclic or
aromatic hydrocarbons, such as, for example, petroleum ether,
hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene,
xylene or decalin; halogenated hydrocarbons, such as, for example,
chlorobenzene, dichlorobenzene, methylene chloride, chloroform,
carbon tetrachloride, dichloroethane, trichloroethane or
tetrachloroethylene; ethers, such as diethyl ether, diisopropyl
ether, methyl tert-butyl ether, methyl tert-amyl ether, dioxane,
tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane,
diethylene glycol dimethyl ether or anisole; alcohols, such as
methanol, ethanol, n- or i-propanol, n-, iso-, sec- or
tert-butanol, ethane-diol, propane-1,2-diol, ethoxyethanol,
methoxyethanol, diethylene glycol mono-methyl ether, diethylene
glycol monoethyl ether; water.
[0317] When carrying out the process (E) according to the
invention, the reaction temperatures can be varied within a
relatively wide range. In general, the process is carried out at
temperatures between 0.degree. C. and +140.degree. C., preferably
between 50.degree. C. and +100.degree. C.
[0318] When carrying out the process (E) according to the
invention, the boronic acid of the formula (X) in which Ar.sup.2'
is as defined above and compounds of the formula (II) in which
Ar.sup.1, X, Y, Z, m, n and Hal are each as defined above are
employed in a molar ratio of from 1:1 to 3:1, preferably from 1:1
to 2:1. In general from 0.005 to 0.5 mol, preferably from 0.01 to
0.1 mol, of catalyst are employed per mole of the compound of the
formula (I.sup.1). The base is generally employed in excess.
[0319] The process (F) is characterized in that compounds of the
formula (I) in which Ar, X, Y, Z, m and n are each as defined above
and K represents oxygen are reacted with sulphurizing agents, if
appropriate in the presence of a diluent.
[0320] The sulphurizing agents to be used are known chemicals for
synthesis such as, for example, phosphorus pentasulphide or
2,4-bis-(4-methoxyphenyl)-1,2,3,4-dithiaphosphetane-2,4-disulphide
(Lawesson's reagent).
[0321] Suitable diluents for the process (F) according to the
invention are all solvents which are inert towards the
abovementioned reagents. Preference is given to using hydrocarbons,
such as, for example, benzine, benzene, toluene, xylene and
tetralin, furthermore halogenated hydrocarbons, such as methylene
chloride, chloroform, chlorobenzene and o-dichlorobenzene, ethers,
such as tetrahydrofuran, dioxane, diisopropyl ether or methyl
tert-butyl ether.
[0322] When carrying out process (F) according to the inventnion,
the reaction temperatures can be varied within a relatively wide
range. In general, the process is carried out at temperatures
between 0.degree. C. and 250.degree. C., preferably between
40.degree. C. and 200.degree. C.
[0323] When carrying out the process (F) according to the
invention, the starting materials of the formula (I) and the
abovementioned reagents are generally in each case employed in
approximately equivalent amounts. However, it is also possible to
employ a relatively large excess of up to 5 mol of the
abovementioned reagents. Work-up is carried out by customary
methods.
[0324] The active compounds according to the invention are
particuliarly suitable for use as defoliants, desiccants,
haulm-killers and, especially, as weed-killers. By weeds, in the
broadest sense, are to be understood all plants which grow in
locations where they are undesired. Whether the substances
according to the invention act as total or selective herbicides
depends essentially on the amount used.
[0325] The dosages of the active compounds according to the
invention required for weed control are between 0.001 and 10 kg/ha,
preferably between 0.005 and 5 kg/ha.
[0326] The active compounds according to the invention can be used,
for example, in connection with the following plants:
[0327] 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.
[0328] Dicotyledonous crops of the geneera: Arachis, Beta,
Brassica, Cucumis, Cucurbita, Helianthus, Daucus, Glycine,
Gossypium, Ipomoea, Lactuca, Linum, Lycopersicon, Nicotiana,
Phaseolus, Pisum, Solanum, Vicia.
[0329] 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.
[0330] Monocotyledonous crops of the genera: Allium, Ananas,
Asparagus, Avena, Hordeum, Oryza, Panicum, Saccharum, Secale,
Sorghum, Triticale, Triticum, Zea.
[0331] According to the invention, it is possible to treat all
plants and parts of plants. By plants are to be understood here 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
breeding and optimization methods or by biotechnological and
genetic engineering methods or combinations of these methods,
including the transgenic plants and including plant cultivars which
can or cannot be protected by plant breeders certificates. Parts of
plants are to be understood as meaning all above-ground and
below-ground parts and organs of plants, such as shoot, leaf,
flower and root, examples which may be mentioned being leaves,
needles, stems, trunks, flowers, shoot-bodies, fruits and seeds and
also roots, tubers and rhizomes. Parts of plants also include
harvested plants and vegetative and generative propagation
material, for example seedlings, tubers, rhizomes, cuttings and
seeds.
[0332] The treatment of the plants and parts of plants according to
the invention with the active compounds is carried out directly or
by action on their environment, habitat or storage area according
to customary treatment methods, for example by dipping, spraying,
evaporating, atomizing, broadcasting, brushing-on and, in the case
of propagation material, in particular in the case of seeds,
furthermore by one- or multi-layer coating.
[0333] However, the use of the active compounds according to the
invention is in no way restricted to these generea, but also
extends in the same manner to other plants. In the use of the
active compounds according to the invention, particular emphasis is
given to the use in connection with transgenic plants, since in
this case synergistic activity increases may be observed.
[0334] The compounds are suitable, depending on the concentration,
for the total control of weeds, for example on industrial terrain
and rail tracks, and on paths and squares with or without tree
plantings. Equally, the compounds can be employed for controlling
weeds in perennial cultures, for example forests, decorative tree
plantings, orchards, vineyards, citrus groves, nut orchards, banana
plantations, coffee plantations, tea plantations, rubber
plantations, oil palm plantations, cocoa plantations, soft fruit
plantings and hopfields, on lawns, turf and pasture-land, and for
the selective control of weeds in annual crops.
[0335] The active compounds according to the invention are highly
suitable for the selective control of monocotyledonous weeds in
dicotyledonous crops by the pre- and post-emergence method. They
can be used very successfully, for example, for the control of
harmful grasses in cotton or sugar beet.
[0336] The active compounds can be converted into the customary
formulations, such as solutions, emulsions, wettable powders,
suspensions, powders, dusting agents, pastes, soluble powders,
granules, suspo-emulsion concentrates, natural and synthetic
materials impregnated with active compound and very fine capsules
and polymeric substances.
[0337] These formulations are prepared in a known manner, for
example by mixing the active compounds with extenders, that is
liquid solvents and/or solid carriers, if appropriate with the use
of surfactants, that is emulsifiers and/or dispersants and/or
foam-formers.
[0338] 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 chlorobenzene,
chloroethylenes or methylene chloride, aliphatic hydrocarbons, such
as cyclohexane or paraffins, for example mineral oil fractions,
mineral or 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 dimethylsulphoxide,
and also water.
[0339] Suitable solid carriers are:
[0340] 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, as well as synthetic granules of inorganic
and organic meals, and granules of organic material such as
sawdust, coconut shells, maize cobs and tobacco stalks; suitable
emulsifiers and/or foam-formers are: for example nonionic and
anionic emulsifiers, such as polyoxyethylene fatty acid esters,
polyoxyethylene fatty alcohol ethers, for example alkylaryl
polyglycol ethers, alkylsulphonates, alkyl sulphates,
arylsulphonates and protein hydrolysates; suitable dispersants are:
for example lignin-sulphite waste liquors and methylcellulose.
[0341] Tackifiers such as carboxymethylcellulose and natural and
synthetic polymers in the form of powders, granules or latices,
such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as
well as natural phospholipids, such as cephalins and lecithins, and
synthetic phospholipids, can be used in the formulations. Other
additives can be mineral and vegetable oils.
[0342] It is possible to use colorants such as inorganic pigments,
for example iron oxide, titanium oxide and Prussian Blue, and
organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and
metal phthalocyanine dyestuffs, and trace nutrients such as salts
of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
[0343] The formulations in general contain between 0.1 and 95% by
weight of active compound, preferably between 0.5 and 90%, and in
addition extenders and/or surfactants.
[0344] The active compound according to the invention can be
present in its commercially available formulations and in the use
forms, prepared from these formulations, as a mixture with other
active compounds, such as insecticides, attractants, sterilizing
agents, bactericides, acaricides, nematicides, fungicides,
growth-regulating substances or herbicides. The insecticides
include, for example, phosphates, carbamates, carboxylates,
chlorinated hydrocarbons, phenylureas and substances produced by
microorganisms, inter alia. In preferred embodiments of the present
invention, it is also possible to mix safeners with the compounds
according to the invention, to increase crop plant
compatibility.
[0345] Examples of particularly advantageous mixing components are
the following:
[0346] Fungicides:
[0347] aldimorph, ampropylfos, ampropylfos potassium, andoprim,
anilazine, azaconazole, azoxystrobin,
[0348] benalaxyl, benodanil, behomyl, benzamacril,
benzamacril-isobutyl, bialaphos, binapacryl, biphenyl, bitertanol,
blasticidin-S, bromuconazole, bupirimate, buthiobate,
[0349] calcium polysulphide, capsimycin, captafol, captan,
carbendazim, carboxin, carvon, quinomethionate, chlobenthiazone,
chlorfenazole, chloroneb, chloropicrin, chlorothalonil,
chlozolinate, clozylacon, cufraneb, cymoxanil, cyproconazole,
cyprodinil, cyprofuram,
[0350] debacarb, dichlorophen, diclobutrazole, diclofluanid,
diclomezine, dicloran, diethofencarb, difenoconazole, dimethirimol,
dimethomorph, diniconazole, diniconazole-M, dinocap, diphenylamine,
dipyrithione, ditalimfos, dithianon, dodemorph, dodine, drazoxolon,
edifenphos, epoxiconazole, etaconazole, ethirimol, etridiazole,
[0351] famoxadon, fenapanil, fenarimol, fenbuconazole, fenfuram,
fenitropan, fenpiclonil, fenpropidin, fenpropimorph, fentin
acetate, fentin hydroxide, ferbam, ferimzone, fluazinam,
flumetover, fluoromide, fluquinconazole, flurprimidol, flusilazole,
flusulfamide, flutolanil, flutriafol, folpet, fosetyl-aluminium,
fosetyl-sodium, fthalide, fuberidazole; furalaxyl, furametpyr,
furcarbonil, furconazole, furconazole-cis, furmecyclox,
[0352] guazatine,
[0353] hexachlorobenzene, hexaconazole, hymexazole,
[0354] irmazalil, imibenconazole, iminoctadine, iminoctadine
albesilate, iminoctadine triacetate, iodocarb, ipconazole,
iprobenfos (IBP), iprodione, irumamycin, isoprothiolane,
isovaledione,
[0355] kasugamycin, kresoxim-methyl, copper preparations, such as:
copper hydroxide, copper naphthenate, copper oxychloride, copper
sulphate, copper oxide, oxine-copper and Bordeaux mixture,
[0356] mancopper, mancozeb, maneb, meferimzone, mepanipyrim,
mepronil, metalaxyl, metconazole, methasulfocarb, methfuroxam,
metiram, metomeclam, metsulfovax, mildiomycin, myclobutanil,
myclozolin,
[0357] nickel dimethyldithiocarbamate, nitrothal-isopropyl,
nuarimol,
[0358] ofurace, oxadixyl, oxamocarb, oxolinic acid, oxycarboxim,
oxyfenthiin,
[0359] paclobutrazole, pefurazoate, penconazole, pencycuron,
phosdiphen, pimaricin, piperalin, polyoxin, polyoxorim,
probenazole, prochloraz, procyinidone, propamocarb,
propanosine-sodium, propiconazole, propineb, pyrazophos, pyrifenox,
pyrimethanil, pyroquilon, pyroxyfur, quinconazole, quintozene
(PCNB),
[0360] sulphur and sulphur preparations,
[0361] tebuconazole, tecloftalam, tecnazene, tetcyclacis,
tetraconazole, thiabendazole, thicyofen, thifluzamide,
thiophanate-methyl, thiram, tioxymid, tolclofos-methyl,
tolylfluanid, triadimefon, triadimenol, triazbutil, triazoxide,
trichlamide, tricyclazole, tridemorph, triflumizole, triforine,
triticonazole,
[0362] uniconazole,
[0363] validamycin A, vinclozolin, viniconazole,
[0364] zarilamide, zineb, ziram and also
[0365] Dagger G,
[0366] OK-8705,
[0367] OK-8801,
[0368]
.A-inverted.-(1,1-dimethylethyl)--(2-phenoxyethyl)-1H-1,2,4-triazol-
e-1-ethanol,
[0369]
.A-inverted.-(2,4-dichlorophenyl)--fluoro-3-propyl-1H-1,2,4-triazol-
e-1-ethanol,
[0370]
.A-inverted.-(2,4-dichlorophenyl)--methoxy-V-methyl-1H-1,2,4-triazo-
le-1-ethanol,
[0371]
.A-inverted.-(5-methyl-1,3-dioxan-5-yl)--[[4-(trifluoromethyl)-phen-
yl]-methylene]-1H-1,2,4-triazole-1-ethanol,
[0372]
(5RS,6RS)-6-hydroxy-2,2,7,7-tetramethyl-5-(1H-1,2,4-triazol-1-yl)-3-
-octanone,
[0373]
(E)-.A-inverted.-(methoxyimino)-N-methyl-2-phenoxy-phenylacetamide,
[0374] 1-isopropyl
{2-methyl-1-[[[1-(4-methylphenyl)-ethyl]-amino]-carbony-
l]-propyl}-carbamate,
[0375] 1-(2,4-dichlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-ethanone
O-(phenylmethyl)-oxime,
[0376] 1-(2-methyl-1-naphthalenyl)-1H-pyrrole-2,5-dione,
[0377]
1-(3,5-dichlorophenyl)-3-(2-propenyl)-2,5-pyrrolidinedione,
[0378] 1-[(diiodomethyl)-sulphonyl]-4-methyl-benzene,
[0379]
1-[[2-(2,4-dichlorophenyl)-1,3-dioxolan-2-yl]-methyl]-1H-imidazole,
[0380]
1-[[2-(4-chlorophenyl)-3-phenyloxiranyl]-methyl]-1H-1,2,4-triazole,
[0381]
1-[1-[2-[(2,4-dichlorophenyl)-methoxy]-phenyl]-ethenyl]-1H-imidazol-
e,
[0382] 1-methyl-5-nonyl-2-(phenylnethyl)-3-pyrrolidinole,
[0383]
2',6'-dibromo-2-methyl-4'-trifluoromethoxy-4'-trifluoro-methyl-1,3--
thiazole-5-carboxanilide,
[0384]
2,2-dichloro-N-[1-(4-chlorophenyl)-ethyl]-1-ethyl-3-methyl-cyclopro-
panecarboxamide,
[0385] 2,6-dichloro-5-(methylthio)-4-pyrimidinyl-thiocyanate,
[0386] 2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide,
[0387]
2,6-dichloro-N-[[4-(trifluoromethyl)-phenyl]-methyl]-benzamide,
[0388] 2-(2,3,3-triiodo-2-propenyl)-2H-tetrazole,
[0389]
2-[(1-methylethyl)sulphonyl]-5-(trichloromethyl)-1,3,4-thiadiazole,
[0390]
2-[[6-deoxy-4-O-(4-O-methyl--D-glycopyranosyl)-.alpha.-D-glucopyran-
osyl]-amino]-4-methoxy-1H-pyrrolo[2,3-d]pyrimidine-5-carbonitrile,
[0391] 2-aminobutane,
[0392] 2-bromo-2-(bromomethyl)-pentanedinitrile,
[0393]
2-chloro-N-(2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl)-3-pyridineca-
rboxamide,
[0394]
2-chloro-N-(2,6-dimethylphenyl)-N-(isothiocyanatomethyl)-acetamide,
[0395] 2-phenylphenol (OPP),
[0396]
3,4-dichloro-1-[4-(difluoromethoxy)-phenyl]-1H-pyrrole-2,5-dione,
[0397]
3,5-dichloro-N-[cyano-[(1-methyl-2-propynyl)-oxy]-methyl]-benzamide-
,
[0398] 3-(1,1-dimethylpropyl-1-oxo-1H-indene-2-carbonitrile,
[0399]
3-[2-(4-chlorophenyl)-5-ethoxy-3-isoxazolidinyl]-pyridine,
[0400]
4-chloro-2-cyano-N,N-dimethyl-5-(4-methylphenyl)-1H-imidazole-1-sul-
phonamide,
[0401] 4-methyl-tetrazolo[1,5-a]quinazolin-5(4H)-one,
[0402]
8-(1,1-dimethylethyl)-N-ethyl-N-propyl-1,4-dioxaspiro[4.5]decane-2--
methanamine,
[0403] 8-hydroxyquinoline sulphate,
[0404] 9H-xanthene-2-[(phenylamino)-carbonyl]-9-carboxylic
hydrazide,
[0405]
bis-(1-methylethyl)-3-methyl-4-[(3-methylbenzoyl)-oxy]-2,5-thiophen-
edicarboxylate,
[0406]
cis-1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-cycloheptanol,
[0407]
cis-4-[3-[4-(1,1-dimethylpropyl)-phenyl-2-methylpropyl]-2,6-dimethy-
l-morpholinehydrochloride,
[0408] ethyl [(4-chlorophenyl)-azo]-cyanoacetate,
[0409] potassium hydrogen carbonate,
[0410] methanetetrathiol sodium salt,
[0411] methyl
1-(2,3-dihydro-2,2-dimethyl-1H-inden-1-yl)-1H-imidazole-5-ca-
rboxylate,
[0412] methyl
N-(2,6-dimethylphenyl)-N-(5-isoxazolylcarbonyl)-DL-alaninate- ,
[0413] methyl
N-(chloroacetyl)-N-(2,6-dimethylphenyl)-DL-alaninate,
[0414]
N-(2,3-dichloro-4-hydroxyphenyl)-1-methyl-cyclohexanecarboxamide,
[0415]
N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-furanyl)-ace-
tamide,
[0416]
N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-thienyl)-ace-
tamide,
[0417]
N-(2-chloro-4-nitrophenyl)-4-methyl-3-nitro-benzenesulphonamide,
[0418]
N-(4-cyclohexylphenyl)-1,4,5,6-tetrahydro-2-pyrimidineamine,
[0419] N-(4-hexylphenyl)-1,4,5,6-tetrahydro-2-pyrimidineamine,
[0420]
N-(5-chloro-2-methylphenyl)-2-methoxy-N-(2-oxo-3-oxazolidinyl)-acet-
amide,
[0421] N-(6-methoxy-3-pyridinyl)-cyclopropanecarboxamide,
[0422]
N-[2,2,2-trichloro-1-[(chloroacetyl)-amino]-ethyl)-benzamide,
[0423]
N-[3-chloro-4,5-bis(2-propinyloxy)-phenyl]-N'-methoxy-methanimidami-
de,
[0424] N-formyl-N-hydroxy-DL-alanine-sodium salt,
[0425] O,O-diethyl
[2-(dipropylamino)-2-oxoethyl]-ethylphosphoramidothioat- e,
[0426] O-methyl S-phenyl phenylpropylphosphoramidothioate,
[0427] S-methyl 1,2,3-benzothiadiazole-7-carbothioate,
[0428] spiro[2H]-1-benzopyrane-2,1'(3'H)-isobenzofuran]-3'-one,
[0429] Bactericides:
[0430] bronopol, dichlorophen, nitrapyrin, nickel
dimethyldithiocarbamate, kasugamycin, octhilinone, furancarboxylic
acid, oxytetracyclin, probenazole, streptomycin, tecloftalam,
copper sulphate and other copper preparations.
[0431] Insecticides/acaricides/nematicides:
[0432] abamectin, acephate, acetamiprid, acrinathrin, alanycarb,
aldicarb, aldoxycarb, alpha-cypermethrin, alphamethrin, amitraz,
avermectin, AZ 60541, azadirachtin, azamethiphos, azinphos A,
azinphos M, azocyclotin,
[0433] Bacillus popilliae, Bacillus sphaericus, Bacillus subtilis,
Bacillus thuringiensis, baculoviruses, Beauveria bassiana,
Beauveria tenella, bendiocarb, benfuracarb, bensultap, benzoximate,
betacyfluthrin, bifenazate, bifenthrin, bioethanomethrin,
bioperrnethrin, BPMC, bromophos A, bufencarb, buprofezin,
butathiofos, butocarboxim, butylpyridaben,
[0434] cadusafos, carbaryl, carbofuran, carbophenothion,
carbosulfan, cartap, chloethocarb, chlorethoxyfos, chlorfenapyr,
chlorfenvinphos, chlorfluazuron, chlormephos, chlorpyrifos,
chlorpyrifos M, chlovaporthrin, cis-resmethrin, cispermethirin,
clocythrin, cloethocarb, clofentezine, cyanophos, cycloprene,
cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin,
cyromazine,
[0435] deltamethrin, demeton M, demeton S, demeton-S-methyl,
diafenthiuron, diazinon, dichlorvos, diflubenzuron, dimethoat,
dimethylvinphos, diofenolan, disulfoton, docusat-sodium,
dofenapyn,
[0436] eflusilanate, emamectin, empenthrin, endosulfan,
Entomopfthora spp., esfenvalerate, ethiofencarb, ethion,
ethoprophos, etofenprox, etoxazole, etrimfos,
[0437] fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion,
fenothiocarb, fenoxacrim, fenoxycarb, fenpropathrin, fenpyrad,
fenpyrithrin, fenpyroximate, fenvalerate, fipronil, fluazinamn,
fluazuron, flubrocythrinate, flucycloxuron, flucythrinate,
flufenoxuron, flutenzine, fluvalinate, fonophos, fosmethilan,
fosthiazate, fubfenprox, furathiocarb,
[0438] granulosis viruses,
[0439] halofenozide, HCH, heptenophos, hexaflumuron, hexythiazox,
hydroprene,
[0440] imidacloprid, isazofos, isofenphos, isoxathion,
ivermectin,
[0441] lambda-cyhalothrin, lufenuron,
[0442] malathion, mecarbam, metaldehyde, methamidophos,
Metharhizium anisopliae, Metharhizium flavoviride, methidathion,
methiocarb, methomyl, methoxyfenozide, metolcarb, metoxadiazone,
mevinphos, milbemectin, monocrotophos,
[0443] naled, nitenpyram, nithiazine, novaluron, nuclear
polyhedrosis viruses,
[0444] omethoat, oxamyl, oxydemethon M,
[0445] Paecilomyces fumosoroseus, parathion A, parathion M,
permethrin, phenthoat, phorat, phosalone, phosmet, phosphamidon,
phoxim, pirimicarb, pirimiphos A, pirimniphos M, profenofos,
promecarb, propoxur, prothiofos, prothoat, pymetrozine, pyraclofos,
pyresmethrin, pyrethrum, pyridaben, pyridathion, pyrimidifen,
pyriproxyfen,
[0446] quinalphos,
[0447] ribavirin,
[0448] salithion, sebufos, silafluofen, spinosad, sulfotep,
sulprofos,
[0449] tau-fluvalinate, tebufenozide, tebufenpyrad, tebupirimiphos,
teflubenzuron, tefluthrin, temephos, temivinphos, terbufos,
tetrachlorvinphos, theta-cypermethrin, thiamethoxam, thiapronil,
thiatriphos, thiocyclam hydrogen oxalate, thiodicarb, thiofanox,
thuringiensin, tralocythrin, tralomethrin, triarathene, triazamate,
triazophos, triazuron, trichlophenidine, trichlorfon, triflumuron,
trimethacarb,
[0450] vamidothion, vaniliprole, Verticillium lecanii,
[0451] YI 5302,
[0452] zeta-cypermethrin, zolaprofos,
[0453]
(1R-cis)-[5-(phenyhnethyl)-3-furanyl]-methyl-3-[(dihydro-2-oxo-3(2H-
)-furanylidene)-methyl]-2,2-dimethylcyclopropanecarboxylate,
[0454]
(3-phenoxyphenyl)-methyl-2,2,3,3-tetramethylcyclopropanecarboxylate-
,
[0455]
1-[(2-chloro-5-thiazolyl)methyl]tetrahydro-3,5-dimethyl-N-nitro-1,3-
,5-triazine-2(1H)-imine,
[0456]
2-(2-chloro-6-fluorophenyl)-4-[4-(1,1-dimethylethyl)phenyl]-4,5-dih-
ydro-oxazole,
[0457] 2-(acetlyoxy)-3-dodecyl-1,4-naphthalenedione,
[0458]
2-chloro-N-[[[4-(1-phenylethoxy)-phenyl]-amio]-carbonyl]-benzamide,
[0459]
2-chloro-N-[[[4-(2,2-dichloro-1,1-difluoroethoxy)-phenyl]-amino]-ca-
rbonyl]-benzamide,
[0460] 3-methylphenyl propylcarbamate
[0461]
4-[4-(4-ethoxyphenyl)-4-methylpentyl]-1-fluoro-2-phenoxy-benzene,
[0462]
4-chloro-2-(1,1-dimethylethyl)-5-[[2-(2,6-dimethyl-4-phenoxyphenoxy-
)ethyl]thio]-3(2H)-pyridazinone,
[0463]
4-chloro-2-(2-chloro-2-methylpropyl)-5-[(6-iodo-3-pyridinyl)methoxy-
]-3(2H)-pyridazinone,
[0464]
4-chloro-5-[(6-chloro-3-pyridinyl)methoxy]-2-(3,4-dichlorophenyl)-3-
(2H)-pyridazinone,
[0465] Bacillus thuringiensis strain EG-2348,
[0466] [2-benzoyl-1-(1,1-dimethylethyl)-hydrazinobenzoic acid,
[0467]
2,2-dimethyl-3-(2,4-dichlorophenyl)-2-oxo-1-oxaspiro[4.5]dec-3-en-4-
-yl butanoate,
[0468]
[3-[(6-chloro-3-pyridinyl)methyl]-2-thiazolidinylidene]-cyanamide,
[0469]
dihydro-2-(nitromethylene)-2H-1,3-thiazine-3(4H)-carboxaldehyde,
[0470] ethyl
[2-[[1,6-dihydro-6-oxo-1-(phenyhnethyl)-4-pyridazinyl]oxy]eth-
yl]-carbamate,
[0471] N-(3,4,4-trifluoro-1-oxo-3-butenyl)-glycine,
[0472]
N-(4-chlorophenyl)-3-[4-(difluoromethoxy)phenyl]-4,5-dihydro-4-phen-
yl-1H-pyrazole-1-carboxamide,
[0473]
N-[(2-chloro-5-thiazolyl)methyl]-N'-methyl-N"-nitro-guanidine,
[0474]
N-methyl-N'-(1-methyl-2-propenyl)-1,2-hydrazinedicarbothioamide,
[0475] N-methyl-N'-2-propenyl-1,2-hydrazinedicarbothioamide,
[0476] O,O-diethyl
[2-(dipropylamino)-2-oxoethyl]-ethylphosphoramidothioat- e.
[0477] Herbicides:
[0478] acetochlor, acifluorfen(-sodium), aclonifen, alachlor,
alloxydim(-sodium), ametryne, amidochlor, amidosulfuron, anilofos,
asulam, atrazime, azafenidin, azimsulfuron, benazolin(-ethyl),
benfuresate, bensulfuron(-methyl), bentazone, benzobicyclon,
benzofenap, benzoylprop(-ethyl), bialaphos, bifenox,
bispyribac(-sodium), bromobutide, bromofenoximn, bromoxynil,
butachlor, butroxydim, butylate, cafenstrole, caloxydim,
carbetamide, carfentrazone(-ethyl), chlomethoxyfen, chloramben,
chloridazon, chlorimuron(-ethyl), chiornitrofen, chlorsulfuron,
chlortoluron, cinidon(-ethyl), cinmethylin, cinosulfuron,
elefoxydim, clethodim, elodinafop(-propargyl), clomazone,
clomeprop, clopyralid, clopyrasulfuron(-methyl),
cloransulam(-methyl), cumyluron, cyanazine, cybutryne, cycloate,
cyclosulfamuron, cycloxydim, cyhalofop(-butyl), 2,4-D, 2,4-DB,
2,4-DP, desmedipham, diallate, dicamba, diclofop(-methyl),
diclosulam, diethatyl(-ethyl), difenzoquat, diflufenican,
diflufenzopyr, dimefuron, dimepiperate, dimethachlor,
dimnethametryn, dimethenamid, dimnexyflam, dinitramine, diphenamid,
diquat, dithiopyr, diuron, dyrnron, epropodan, EPTC, esprocarb,
ethalfluralin, etharnetsulfuron(-methyl), ethoflmesate, ethoxyfen,
ethoxysulfuron, etobenzanid, enoxaprop(-P-ethyl), fentrazamide,
flamprop(-isopropyl), flamprop(-isopropyl-L), flamprop(-methyl),
flazasulfuron, florasulam, fluazifop(-P-butyl), fluazolate,
flucarbazone, flufenacet, flumetsulam, flumiclorac(-pentyl),
flumioxazin, flumipropyn, flumetsulam, fluometuron,
fluorochloridone, fluoroglycofen(-ethyl), flupoxam, flupropacil,
flurpyrsulfuiron(-methyl, -sodium), flurenol(-butyl), fluridone,
fluroxypyr(-meptyl), flurprimidol, flurtamone, fluthiacet(-methyl),
fluthiamide, fomesafen, glufosinate(-ammonium),
glyphosate(-isopropylammonium), halosafen, haloxyfop(-ethoxyethyl),
haloxyfop(-P-methyl), hexazinone, imazarnethabenz(-methyl),
imazamethapyr, imazamox, imazapic, imazapyr, imazaquin,
imazethapyr, imazosulfuron, iodosulfuron(-methyl, -sodium),
ioxynil, isopropalin, isoproturon, isouron, isoxaben,
isoxachlortole, isoxaflutole, isoxapyrifop, lactofen, lenacil,
linuron, MCPA, MCPP, mefenacet, mesotrione, metamitron,
metazachlor, methabenzthiazuron, metobenzuron, metobromuron,
(alpha-)metolachlor, metosulam, metoxuron, metribuzin,
metsulfuron(-methyl), molinate, monolinuron, naproanilide,
napropamide, neburon, nicosulfuron, norflurazon, orbencarb,
oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefone,
oxyfluorfen, paraquat, pelargonic acid, pendimethalin, pendralin,
pentoxazone, phenmedipham, piperophos, pretilachlor,
primisulfuron(-methyl), prometryn, propachlor, propanil,
propaquizafop, propisochlor, propyzamide, prosulfocarb,
prosulfuron, pyraflufen(-ethyl), pyrazolate,
pyrazosulfaron(-ethyl), pyrazoxyfen, pyribenzoxim, pyributicarb,
pyridate, pyriminobac(-methyl), pyrithiobac(-sodium), quinchlorac,
quinnerac, quinoclamine, quizalofop(-P-ethyl),
quizalofop(-P-tefuryl), rimsulfuron, sethoxydim, simazine,
simetryn, sulcotrione, sulfentrazone, sulfometuron(-methyl),
sulfosate, sulfosulfuron, tebutam, tebuthiuron, tepraloxydim,
terbuthylazine, terbutryn, thenylchlor, thiafluamide, thiazopyr,
thidiazimin, thifensulfuron(-methyl), thiobencarb, tiocarbazil,
tralkoxydim, triallate, triasulfuron, tribenuron(-methyl),
triclopyr, tridiphane, trifluralin and triflusulfuron.
[0479] Furthermore, the active compound according to the invention,
in its commercial formulations and in the use forms prepared from
these formulations, can be present as a mixture with synergists.
Synergists are compounds which increase the activity of the active
compounds without it being necessary for the added synergist to be
active itself.
[0480] The active compound content of the use forms prepared from
the commercial formulations can vary within wide ranges. The
concentration of active compound in the use forms can be from
0.0000001 to 95% by weight of active compound, preferably between
0.0001 and 1% by weight.
[0481] Application is carried out in a customary manner adapted to
the use forms.
[0482] The active compounds are furthermore suitable for
controlling animal pests, preferably arthropods and nematodes, in
particular insects and arachnids, which are encountered in
agriculture, in forestry, in the protection of stored products and
of materials, and in the hygiene sector. They are active against
normally sensitive and resistant species and against all or some
stages of development. The above-mentioned pests include:
[0483] From the order of the Isopoda, for example, Oniscus asellus,
Armadillidium vulgare and Porcelijo scaber.
[0484] From the order of the Diplopoda, for example,
[0485] Blaniulus guttulatus.
[0486] From the order of the Chilopoda, for example, Geophilus
carpophagus and Scutigera spec.
[0487] From the order of the Symphyla, for example, Scutigerella
immaculata.
[0488] From the order of the Thysanura, for example, Lepisma
saccharina.
[0489] From the order of the Collembola, for example, Onyclhiurus
armatus.
[0490] From the order of the Blattaria or Orthoptera, for example,
Blatta orientalis, Periplaneta americana, Leucophaea maderae,
Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta
migratoria migratorioides, Melanoplus differentialis and
Schistocerca gregaria.
[0491] From the order of the Dermaptera, for example, Forficula
auricularia.
[0492] From the order of the Isoptera, for example, Reticulitermes
spp.
[0493] From the order of the Anoplura, for example, Phylloxera
vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus
spp. and Linognathus spp.,
[0494] From the order of the Mallophaga, for example, Trichodectes
spp. and Damalinea spp.
[0495] From the order of the Thysanoptera, for example,
Franklcliniella occidentalis, Hercinothrips femoralis, Thrips palmi
and Thrips tabaci.
[0496] From the ordeer of the Heteroptera, for example, Eurygaster
spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius,
Rhodnius prolixus and Triatoma spp.
[0497] From the order of the Homoptera, for example, Aleurodes
brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis
gossypii, Brevicoryne brassicae, Cryptomyzus nibis, Aphis fabae,
Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Phylloxera
vasturix, 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.
[0498] From the order of the Lepidoptera, for example, Pectinophora
gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis
blancardella, Hyponomeuta padella, Plutella maculipennis, Plutella
xylostella, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria
spp., Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis
spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp.,
Spodoptera exigua, Mamestra brassicae, Panolis flammea, Prodenia
litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella,
Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella,
Galleria mellonella, Tineola bisselliella, Tinea pellionella,
Hofmnannophila pseudospretella, Cacoecia podana, Capua reticulana,
Choristoneura fumiferana, Clysia ambiguella, Homona magnanima,
Tortrix viridana, Cnaphalocerus spp. and Aulema oryzae.
[0499] From the order of the Coleoptera, for example, Anobium
punctatum, Rhizopertha dominica, Acanthoscelides obtectus,
Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata,
Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala,
Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis,
Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus,
Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica,
Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp.,
Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus,
Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes
spp., Conoderus spp., Melolontha melolontha, Amphimallon
solstitialis, Costelytra zealandica and Lissorhoptus
oryzophilus.
[0500] From the order of the Hymenoptera, for example, Diprion
spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis and Vespa
spp.
[0501] From the order of the Diptera, for example, Aedes spp.,
Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp.,
Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia
spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Liriomyza
spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp.,
Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp.,
Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula
paludosa, Hylemnia spp. and Liviomyza spp.
[0502] From the order of the Siphonaptera, for example, Xenopsylla
cheopis and Ceratophyllus spp.
[0503] From the order of the Arachnida, for example, Scorpio maurus
and Latrodectus mactans.
[0504] From the order of the Acarina, for example, Acarus siro,
Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes
ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp.,
Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp.,
Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia
praetiosa, Panonychus spp., Tetranychus spp., Hemitarsonemus spp.
and Brevipulpus spp.
[0505] The phytoparasitic nematodes include, for example,
Pratylenchus spp; Radopholus similis, Ditylenchus dipsaci,
Tylenchulus semi penetrans, Heteroderma spp., Globodera spp.,
Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema
spp., Trichodorus spp. and Bursaphelenchus spp.
[0506] The active compounds according to the invention have high
insecticidal and acaricidal activity after foliar and soil
application.
[0507] At certain concentrations or application rates, the
compounds according to the invention also have fungicidal action.
Furthermore, they can be used as microbicides or antimycotics.
[0508] When used against hygiene pests and pests of stored
products, the active compound has excellent residual activity on
wood and clay, and by good stability to alkali on limed
substrates.
[0509] The active compounds according to the invention act not only
against plant, hygiene and stored product pests, but also in the
veterinary medicine sector against animal parasites
(ectoparasites), such as hard ticks, soft ticks, mange mites, leaf
mites, flies (biting and licking), parasitic fly larvae, lice, hair
lice, feather lice and fleas. These parasites include:
[0510] From the order of the Anoplurida, for example, Haematopinus
spp., Linognathus spp., Pediculus spp., Phtirus spp. and
Solenopotes spp.
[0511] From the order of the Mallophagida and the suborders
Amblycerina and Ischnocerina, for example, Trimenopon spp., Menopon
spp., Trinoton spp., Bovicola spp., Wemeckiella spp., Lepikentron
spp., Damalina spp., Trichodectes spp. and Felicola spp.
[0512] From the order of the Diptera and the suborders Nematocerina
and Brachycerina, for example, Aedes spp., Anopheles spp., Culex
spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia
spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus
spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula
spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp.,
Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia
spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus
spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp.,
Lipoptena spp. and Melophagus spp.
[0513] From the order of the Siphonapterida, for example Pulex
spp., Ctenocephalides spp., Xenopsylla spp. and Ceratophyllus
spp.
[0514] From the order of the Heteropterida, for example, Cimex
spp., Triatoma spp., Rhodnius spp. and Panstrongylus spp.
[0515] From the order of the Blattarida, for example Blatta
orientalis, Periplaneta americana, Blattela germanica and Supella
spp.
[0516] From the subclass of the Acaria (Acarida) and the orders of
the Meta- and Mesostigmata, for example, Argas spp., Ornithodorus
spp., Otobius spp., Ixodes spp., Amblyomma spp., Boophilus spp.,
Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus
spp., Dermanyssus spp., Raillietia spp., Pneumonyssus spp.,
Stemostoma spp. and Varroa spp.
[0517] From the order of the Actinedida (Prostigmata) und Acaridida
(Astigmata), for example, Acarapis spp., Cheyletiella spp.,
Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp.,
Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp.,
Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes
spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres
spp., Knemidocoptes spp., Cytodites spp. and Laminosioptes spp.
[0518] The active compounds of the formula (I) according to the
invention are also suitable for controlling arthropods which infest
agricultural productive livestock, such as, for example, cattle,
sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits,
chickens, turkeys, ducks, geese and bees, other pets, such as, for
example, dogs, cats, caged birds and aquarium fish, and also
so-called test animals, such as, for example, hamsters, guinea
pigs, rats and mice. By controlling these arthropods, cases of
death and reduction in productivity (for meat, milk, wool, hides,
eggs, honey etc.) should be diminished, so that more economic and
easier animal husbandry is possible by use of the active compounds
according to the invention.
[0519] The active compounds according to the invention are used in
the veterinary sector in a known manner by enteral administration
in the form of, for example, tablets, capsules, potions, drenches,
granules, pastes, boluses, the feed-through process and
suppositories, by parenteral administration, such as, for example,
by injection (intramuscular, subcutaneous, intravenous,
intraperitoneal and the like), implants by nasal administration, by
dermal use in the form, for example, of dipping or bathing,
spraying, pouring on and spotting on, washing and powdering, and
also with the aid of molded articles containing the active
compound, such as collars, ear marks, tail marks, limb bands,
halters, marking devices and the like.
[0520] When used for cattle, poultry, pets and the like, the active
compounds of the formula (I) can be used as formulations (for
example powders, emulsions, free-flowing compositions), which
comprise the active compounds in an amount of 1 to 80% by weight,
directly or after 100 to 10,000-fold dilution, or they can be used
as a chemical bath.
[0521] It has furthermore been found that the compounds of the
formula (a) according to the invention also have a strong
insecticidal action against insects which destroy industrial
materials.
[0522] The following insects may be mentioned as examples and as
preferred--but without a limitation:
[0523] Beetles, such as
[0524] Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum,
Xestobium rufovillosum, Ptilinus pecticomis, Dendrobium pertinex,
Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus
africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens,
Trogoxylon aequale, Minthes rugicollis, Xyleborus spec.,
Tryptodendron spec., Apate monachus, Bostrychus capucins,
Heterobostrychus brunneus, Sinoxylon spec., Dinoderus minutus.
[0525] Hymenopterons, such as
[0526] Sirex juvencus, Urocerus gigas, Urocerus gigas taignus,
Urocerus augur
[0527] Termites, such as
[0528] Kalotermes flavicollis, Cryptotermes brevis, Heterotermes
indicola, Reticulitermes flavipes, Reticulitermes santonensis,
Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermnopsis
nevadensis, Coptotermes formosanus.
[0529] Bristletails, such as
[0530] Lepisma saccarina.
[0531] Industrial materials in the present connection are to be
understood as meaning non-living materials, such as, preferably,
plastics, adhesives, sizes, papers and cards, leather, wood and
processed wood products and coating compositions.
[0532] Wood and processed wood products are materials to be
protected, especially preferably, from insect infestation.
[0533] Wood and processed wood products which can be protected by
the agents according to the invention or mixtures comprising these
are to be understood as meaning, for example: building timber,
wooden beams, railway sleepers, bridge components, boat jetties,
wooden vehicles, boxes, pallets, containers, telegraph poles, wood
panelling, wooden windows and doors, plywood, chipboard, joinery or
wooden products which are used quite generally in house-building or
in building joinery.
[0534] The active compounds can be used as such, in the form of
concentrates or in generally customary formulations, such as
powders, granules, solutions, suspensions, emulsions or pastes.
[0535] The formulations mentioned can be prepared in a manner known
per se, for example by mixing the active compounds with at least
one solvent or diluent, emulsifier, dispersing agent and/or binder
or fixing agent, a water repellent, if appropriate siccatives and
UV stabilizers and if appropriate dyestuffs and pigments, and also
other processing auxiliaries.
[0536] The insecticidal compositions or concentrates used for the
preservation of wood and timber products comprise the active
compound according to the invention in a concentration of 0.0001 to
95% by weight, in particular 0.001 to 60% by weight.
[0537] The amount of the compositions or concentrates employed
depends on the nature and occurrence of the insects and on the
medium. The optimum amount employed can be determined for the use
in each case by a series of tests. In general, however, it is
sufficient to employ 0.0001 to 20% by weight, preferably 0.001 to
10% by weight, of the active compound, based on the material to be
preserved.
[0538] Solvents and/or diluents which are used are an
organochemical solvent or solvent mixture and/or an oily or
oil-like organochemical solvent or solvent mixture of low
volatility and/or a polar organochemical solvent or solvent mixture
and/or water, and if appropriate an emulsifier and/or wetting
agent.
[0539] Organochemical solvents which are preferably used are oily
or oil-like solvents having an evaporation number above 35 and a
flash point above 30.degree. C., preferably above 45.degree. C.
Substances which are used as such oily or oil-like water-insoluble
solvents of low volatility are appropriate mineral oils or aromatic
fractions thereof, or solvent mixtures containing mineral oils,
preferably white spirit, petroleum and/or alkylbenzene.
[0540] Mineral oils having a boiling range from 170 to 220.degree.
C., white spirit having a boiling range from 170 to 220.degree. C.,
spindle oil having a boiling range from 250 to 350.degree. C.,
petroleum and aromatics having a boiling range from 160 to
280.degree. C., terpentine oil and the like, are advantageously
employed.
[0541] In a preferred embodiment, liquid aliphatic hydrocarbons
having a boiling range from 180 to 210.degree. C. or high-boiling
mixtures of aromatic and aliphatic hydrocarbons having a boiling
range from 180 to 220.degree. C. and/or spindle oil and/or
monochloronaphthalene, preferably .alpha.-monochloronaphthalene,
are used.
[0542] The organic oily or oil-like solvents of low volatility
which have an evaporation number above 35 and a flashpoint above
30.degree. C., preferably above 45.degree. C., can be replaced in
part by organochemical solvents of high or medium volatility,
providing that the solvent mixture likewise has an evaporation
number above 35 and a flashpoint above 30.degree. C., preferably
above 45.degree. C., and that the insecticide/fungicide mixture is
soluble or emulsifiable in this solvent mixture.
[0543] According to a preferred embodiment, some of the
organochemical solvent or solvent mixture is replaced by an
aliphatic polar organochemical solvent or solvent mixture.
[0544] Aliphatic organochemical solvents containing hydroxyl and/or
ester and/or ether groups, such as, for example, glycol ethers,
esters or the like, are preferably used.
[0545] Organochemical binders which are used in the context of the
present invention are the synthetic resins and/or binding drying
oils which are known per se, are water-dilutable and/or are soluble
or dispersible or emulsifiable in the organochemical solvents
employed, in particular binders consisting of or comprising an
acrylate resin, a vinyl resin, for example polyvinyl acetate,
polyester resin, polycondensation or polyaddition resin,
polyurethane resin, alkyd resin or modified alkyd resin, phenolic
resin, hydrocarbon resin, such as indene-cumarone resin, silicone
resin, drying vegetable oils and/or drying oils and/or physically
drying binders based on a natural and/or synthetic resin.
[0546] The synthetic resin used as the binder can be employed in
the form of an emulsion, dispersion or solution. Bitumen or
bituminous substances can also be used as binders in an amount of
up to 10% by weight. Dyestuffs, pigments, water-repelling agents,
odour correctants and inhibitors or anticorrosive agents and the
like which are known per se can additionally be employed.
[0547] It is preferred according to the invention for the
composition or concentrate to comprise, as the organochemical
binder, at least one alkyd resin or modified alkyd resin and/or one
drying vegetable oil. Alkyd resins having an oil content of more
than 45% by weight, preferably 50 to 68% by weight, are preferably
used according to the invention.
[0548] All or some of the binder mentioned can be replaced by a
fixing agent (mixture) or a plasticizer (mixture). These additives
are intended to prevent evaporation of the active compounds and
crystallization or precipitation. They preferably replace 0.01 to
30% of the binder (based on 100% of the binder employed).
[0549] The plasticizers originate from the chemical classes of
phthalic acid esters, such as dibutyl, dioctyl or benzyl butyl
phthalate, phosphoric acid esters, such as tributyl phosphate,
adipic acid esters, such as di-(2-ethylhexyl) adipate, stearates,
such as butyl stearate or amyl stearate, oleates, such as butyl
oleate, glycerol ethers or higher molecular weight glycol ethers,
glycerol esters and p-toluenesulphonic acid esters.
[0550] Fixing agents are based chemically on polyvinyl alkyl
ethers, such as, for example, polyvinyl methyl ether or ketones,
such as benzophenone or ethylenebenzophenone.
[0551] Possible solvents or diluents are, in particular, also
water, if appropriate as a mixture with one or more of the
abovementioned organochemical solvents or diluents, emulsifiers and
dispersing agents.
[0552] Particularly effective preservation of wood is achieved by
impregnation processes on a large industrial scale, for example
vacuum, double vacuum or pressure processes.
[0553] The ready-to-use compositions can also comprise other
insecticides, if appropriate, and also one or more fungicides, if
appropriate.
[0554] Possible additional mixing components are, preferably, the
insecticides and fungicides mentioned in WO 94/29 268. The
compounds mentioned in this document are an explicit constituent of
the present application.
[0555] Especially preferred mixing partners which may be mentioned
are insecticides, such as chlorpyriphos, phoxim, silafluofin,
alphamethrin, cyfluthrin, cypermethrin, deltamethrin, permethrin,
imidacloprid, NI-25, flufenoxuron, hexaflumuron and triflumuron,
and also fungicides, such as epoxyconazole, hexaconazole,
azaconazole, propiconazole, tebuconazole, cyproconazole,
metconazole, imazalil, dichlorfluanid, tolylfluanid,
3-iodo-2-propinyl-butyl carbamate, N-octyl-isothiazolin-3-one and
4,5-dichloro-N-octylisothiazolin-3-one.
[0556] The active compounds according to the invention can be used
particularly effectively for controlling plant-damaging insects,
such as, for example, against the larvae of the mustard beetle
(Phaedon cochleariae), against the larvae of the green rice
leafhopper (Nephotettix cincticeps) and against the larvae of the
green peach aphid (Myzus persicae).
[0557] In addition to the acaricidal, herbicidal and insecticidal
properties described, a fungicidal activity of the active compounds
according to the invention is noticeable. In both ,in vitro` and
,in vivo` studies, a broad fungicidal effect can be observed.
[0558] Moreover, it was noticed that the active compounds are, in
particular, also suitable for controlling mildew, leaf blotch and
Fusaria on the infected plants.
[0559] The preparation and the use of the active compounds
according to the invention is shown in the Examples below.
PREPARATION EXAMPLES
Example 1
[0560] 72
[0561] (Process A)
[0562] A mixture of 1.2 g of 2-ethoxy-pyrroline and 1 g of
4-chlorobenzoylacetonitrile in 20 ml of toluene is stirred at
100.degree. C. for 1 hour. The resulting ethyl alcohol is distilled
off azeotropically with toluene. After cooling to 20.degree. C.,
the reaction mixture is crystallized by the addition of hexane and
crystals are filtered off with suction.
[0563] This gives 1.1 g (yield: 74% of theory) of
3-(4-chlorophenyl)-3-oxo- -2-pyrrolidin-2-ylidene-propionitrile of
melting point 156-158.degree. C.
Example 2
[0564] 73
[0565] (Process E)
[0566] A solution of 1.85 g of
3-oxo-3-(4-bromophenyl)-2-piperidin-2-ylide- ne-propionitrile in 20
ml of dimethoxyethane, which was prepared at 20.degree. C., is,
under argon as protective gas, admixed with 1 g of
4-chlorophenylboronic acid and 360 mg of
tetrakis(triphenylphosphine)-pal- ladium, and the mixture is
stirred at 20.degree. C. for 15 minutes. 10 ml of 20% strength
Na.sub.2CO.sub.3 solution are then added, and the mixture is heated
at 80.degree. C. for 24 h. The mixture is subsequently acidified
with conc. hydrochloric acid, diluted with water and shaken with
ethyl acetate, and the organic phase is separated off, washed with
water, dried and filtered. The solvent is distilled off from the
filtrate.
[0567] This gives 1.9 g (yield 95% of theory) of
3-(4'-chloro-biphenyl-4-y-
l)-3-oxo-2-piperidin-2-ylidene-propionitrile of melting point
134.degree. C.
Example 3
[0568] 74
[0569] (Process D)
[0570] At 0.degree. C., 1 g of the
3-(4-chlorophenyl)-3-oxo-2-pyrrolidin-2- -ylidene-propionitrile
prepared according to Example 1 is dissolved in 10 ml of THF and
admixed with 0.16 g of NaH (60% pure), and the mixture is heated at
20.degree. C. for four hours. 0.65 g of 2-chloro-5-chloromethyl-
-pyridine is then added, and the mixture is boiled under reflux for
4 hours. 100 mg of diazabicyclooctane (DABCO) are then added, and
the mixture is heated under reflux for another 24 hours. The
reaction mixture is then poured into ice-water, the solid residues
are filtered off with suction, the liquid phase is shaken with
ethyl acetate and the organic phase is then separated off, washed
with water and filtered. The compounds contained in the solution
were separated by column chromatography on a silica gel phase using
the mobile phase hexane/acetone 7:3.
[0571] After evaporation of the solvent, one of the main fractions
gave 0.65 g (yield 44% of theory) of
3-(4-chlorophenyl)-2-[1-(6-chloropyridin--
3-yl-methyl)-pyrrolidin-2-yl]-dene]-3-oxo-propionitrile of melting
point 142-144.degree. C.
Example 4
[0572] 75
[0573] (Process D)
[0574] At 0.degree. C., 1.5 g of
3-(2-chloro-phenyl)-3-oxo-2-pyrrolidin-2-- ylidene-propionitrile
are dissolved in 10 ml of THF and admixed with 0.5 g of NaH (60%
pure), and the mixture is heated at 20.degree. C. for four hours.
1.1 g of 2-chloro-5-chloromethyl-thiazole in 10 ml of THF and 100
mg of diazabicyclooctane (DABCO) are then added, and the mixture is
carefully maintained at room temperature (20.degree. C.) and the
progress of the reaction is monitored by thin-layer chromatography.
The reaction mixture is then poured into ice-water, the solid
residues are filtered off with suction, the liquid phase is shaken
with ethyl acetate and the organic phase is then separated off,
washed with water and filtered. The compounds contained in the
solution were separated by column chromatography on a silica gel
phase using the mobile phase n-hexane/acetone 7:3.
[0575] After evaporation of the solvent, one of the main fractions
gave 0.4 g (yield 13% of theory) of
3-(2-chlorophenyl)-2-[3-(2-chloro-thiazol--
5-yl)-1-(2-chloro-thiazol-5-yl-methyl)pyrrolidin-2-ylidene]-3-oxo-propioni-
trile.
Example 5
[0576] 76
[0577] (Process D)
[0578] At 0.degree. C., 1 g of the
3-(4-chlorophenyl)-3-oxo-2-pyrrolidin-2- -ylidene-propionitrile
prepared according to Example 1 is dissolved in 10 ml of THF and
admixed with 0.3 g of NaH (60% pure), and the mixture is heated to
20.degree. C. for two hours. 0.8 g of chlorobenzoyl chloride in 10
ml of THF is then added, and the mixture is stirred at room
temperature for another 24 hours. The reaction mixture is then
poured into ice-water and extracted with ethyl acetate, the extract
is dried over magnesium sulphate and the solvent is evaporated
under reduced pressure. The residue was chromatographed over silica
gel using n-hexane/acetone 7:3. After evaporation of the solvent,
one of the main fractions gave 0.2 g (yield 14% of theory) of
2-[1-(4-chlorobenzoyl)pyrro-
lidin-2-ylidene]-3-(4-chlorophenyl)-3-oxo-propionitrile of melting
point 218.degree. C.
Example 6
[0579] 77
[0580] (Process A)
[0581] A mixture of 0.9 g of
6-(4-bromo-phenyl)-2-ethoxy-tetrahydropyridin- e and 0.5 g of
chlorobenzoylacetonitrile in 10 ml of toluene is heated to
120.degree. C. and kept at this temperature for two hours. The
reaction products contained in the solution are separated by column
chromatography on a silica gel phase using the mobile phase
methylene chloride/ethyl acetate 5:3.
[0582] After evaporation of the solvent, the main fraction gave 0.9
g (yield 77.6% of theory) of
2-[6-(4-bromo-phenyl)-piperidin-2-ylidene]-3-(-
4-chloro-phenyl)-3-oxo-propionitrile.
Example 7
[0583] 78
[0584] (Intermediates for Process A According to Formula (III);
Comp. No. III-1)
[0585] 63 g of ethyl DL-pyroglutamate in 200 ml of methylene
chloride are added dropwise over a period of 10 minutes to a
solution of 500 ml of triethyloxonium tetrafluoroboronate (Meerwein
salt, as a one molar solution in methylene chloride), and the
mixture is heated under reflux for 24 hours. The solution is then
cooled to 0.degree. C. and carefully admixed with 63 g of sodium
carbonate in 300 ml of water. The reactino product is extracted
with methylene chloride, the organic phase is dried and filtered
and the solvent is subsequently stripped off under waterpump
vacuum.
[0586] This gives 12.5 g (yield 12.9% of theory) of ethyl
5-ethoxy-3,4-dihydro-2H-pyrrole-2-carboxylate. 79
[0587] (Process A)
[0588] A mixture of 6.1 g of the ethyl
5-ethoxy-3,4-dihydro-2H-pyrrole-2-c- arboxylate prepared and 6 g of
chlorobenzoylacetonitrile in 50 ml of toluene is stirred at
100.degree. C. for 1 hour. The resulting ethyl alcohol is
subsequently distilled off azeotropically together with the
toluene. After cooling to 20.degree. C., the reaction product is
crystallized by addition of hexane and filtered off with suction.
The main product is separated by column chromatography on a silica
gel phase using n-hexane/acetone 7:3.
[0589] After evaporation of the solvent, the main fraction gave 6.9
g (yield 67% of theory) of ethyl
5-[2-(4-chloro-phenyl)-1-cyano-2-oxo-ethyl-
idene]-pyrrolidine-2-carboxylate of melting point 108-110.degree.
C.
Example 8
[0590] 80
[0591] 4.8 g of the ethyl
5-[2-(4-chloro-phenyl)-1-cyano-2-oxo-ethylidene]-
-pyrrolidine-2-carboxylate prepared according to Example 7 are, at
40.degree. C., dissolved in 30 ml of ethanol and admixed with 10 ml
of 20% strength NaOH. The mixture is stirred at the stated
temperature for one hour and then concentrated under waterpump
vacuum and adjusted to pH 1-2 using HCl.
[0592] 2.5 g of
5-[2-(4-chloro-phenyl)-1-cyano-2-oxo-ethylidene]-pyrrolidi-
ne-2-carboxylic acid of melting point 134-136.degree. C. are
obtained as residue.
Example 9
[0593] 81
[0594] (Intermediate for Compounds of the Formula (III) According
to Formula (V); Comp. No. V-1)
[0595] 38.5 g of 6-(4-bromo-phenyl)-piperidin-2-one and 31 g of
[2,4-bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane-2,4-disulphide]
(Lawesson's reagent) in 200 ml of anhydrous toluene are heated at
reflux for about 2 hours. The progress of the reaction is monitored
by thin-layer chromatography. The reaction products contained in
the solution are separated by column chromatography on a silica gel
phase using the mobile phase methylene chloride/ethyl acetate
5:3.
[0596] After evaporation of the solvent, the main fraction gave 20
g (yield 50% of theory) of 6-(4-bromo-phenyl)-piperidine-2-thione.
82
[0597] (Intermediate for Process A According to Formula (III))
[0598] At 20.degree. C., 8 g of
6-(4-bromo-phenyl)-piperidine-2-thione are dissolved in 150 ml of
acetone and admixed successively with 10 g of potassium carbonate
and 10 g of methyl iodide. Over a period of 24 hours, during which
the mixture is heated at reflux, the progress of the reaction is
monitored by thin-layer chromatography. After cooling, the solid is
filtered off with suction and the filtrate is concentrated. The
reaction products contained in the solution are separated by column
chromatography on a silica gel phase using the mobile phase
methylene chloride/ethyl acetate 5:3.
[0599] After evaporation of the solvent, the main fraction gave 2.1
g (yield 25% of theory) of
6-(4-bromo-phenyl)-2-methylmercapto-2,3,4,5-tetr- ahydro-pyridine
as a yellow oil.
Example 10
[0600] 83
[0601] (Intermediate for Process A According to Formula (II); Comp.
No. II-1)
[0602] 80 g of ethyl 4-bromobenzoate are initially charged in 2000
ml of dioxane and 50 g of acetonitrile. After addition of 3 drops
of tris-[2-(2-methoxyethoxy)-ethyl]-amine (TDA-1), the mixture is
heated to 90.degree. C. Subsequently, 70 g of potassium
tert-butoxide are added a little at a time, and the mixture is
heated at reflux for three hours. The mixture is then concentrated
under waterpump vacuum, the residue is taken up in water, acidified
using 10% strength HCl, admixed with methylene chloride and
filtered, the methylene chloride phase is extracted with saturated
sodium carbonate solution and the dried organic phase is
concentrated to dryness.
[0603] 82 g (yield 72% of theory) of
3-(4-bromo-phenyl)-3-oxopropionitrile are obtained as residue.
Example 11
[0604] 84
[0605] Under protective gas (argon), 5.84 g of NaH (60% pure) are
initially charged in 147 ml of toluene. At 20.degree. C., 10.51 g
of tert-butyl cyanoacetate (98% pure) in 9 ml of toluene are then
added dropwise, and the mixture is stirred at room temperature for
45 minutes. 18.5 g of 3-nitro-5-trifluoromethyl-benzoyl chloride in
9 ml of toluene are then added dropwise, and the mixture is stirred
for another 24 hours. 168 ml of water are then added carefully, and
the toluene phase is separated off and washed with about 190 ml of
water. The combined aqueous phases are washed twice with methylene
chloride, acidified with 2 N HCl and then again extracted twice
with methylene chloride. The combined organic phases are washed
with water, dried over Na.sub.2SO.sub.4 and concentrated under
waterpump vacuum.
[0606] 13.1 g (yield 53% of theory) of tert-butyl
2-cyano-3-(3-nitro-5-tri- fluoromethyl-phenyl)-3-oxo-propionate are
obtained as residue. 85
[0607] (Intermediate for Process A According to Formula (II); Comp.
No. II-2)
[0608] 13 g of tert-butyl
2-cyano-3-(3-nitro-5-trifluoromethyl-phenyl)-3-o- xo-propionate are
then initially charged in 55 ml of toluene and, at 20.degree. C.,
admixed with 0.07 g of p-toluenesulphonic acid (monohydrate). The
mixture is heated under reflux for two hours and the progress of
the reaction is monitored by thin-layer chromatography. The
solution is subsequently concentrated, and the residue is taken up
in methylene chloride/methanol (99:1) and then fiiltered through
silica gel, and the solvent is stripped off.
[0609] This gives 5.5 g (yield 59% of theory) of
3-(3-nitro-5-trifluoro-ph- enyl)-3-oxo-propionitrile.
Example 12
[0610] 86
[0611] 3.06 g (20 mmol) of 1-methyl-2-chloro-2-pyrroline-iminium
chloride are suspended in 10 ml of toluene. Under protective gas,
1.79 g (19 mmol) of 4-chlorobenzoyl-acetonitrile (as a solution in
30 ml of chloroform) and then 3.06 ml (22 mmol) of triethylamine
(as a solution in 30 ml of chloroform) are added dropwise, in each
case at 0.degree. C. The addition is carried out with effective
cooling. After one hour of stirring at 0.degree. C. and 2 hours of
stirring at room temperature, another 3.06 g of
1-methyl-2-chloro-2-pyrroline-iminium chloride and 4.18 ml of
triethylamine are added at 0.degree. C. The mixture is stirred at
room temperature for 48 hours. The reaction mixture is subsequently
poured into 30 ml of ice-water and extracted three times with in
each case 50 ml of chloroform. The chloroform phase is dried over
magnesium sulphate and then concentrated to dryness.
[0612] The resulting reaction product is separated by column
chromatography on a silica gel phase using the mobile phase
hexane/ethyl acetate 1:1.
[0613] After evaporation of the solvent, the main fraction gave 620
mg (yield 24% of theory) of
3-(4-chloro-phenyl)-3-oxo-2-(-methyl-pyrrolidin--
2-ylidene)-propionitrile of melting point 115.degree. C.
Example 13
[0614] 87
[0615] 1 g of the compound from Example I-1-a-55 are dissolved in
10 ml of toluene, and the mixture is admixed with 1.58 g (3.9 mmol)
of Lawesson's reagent and heated to reflux. After 1 hour, it was no
longer possible to detect starting material by thin-layer
chromatography using the mobile phase hexane/ethyl aceetate. Half
of the solvent was then stripped off and the precipitated crystals
were filtered off with suction. The product which precipitates out
after further concentration is separated by column chromatography
on a silica gel phase using the mobile phase hexane/ethyl
acetate.
[0616] After evaporation of the solvent, the main fraction gave
0.560 g (yield 53% of theory) of
3-(4-chlorophenyl)-3-thio-2-piperidin-2-ylidene-- propionitrile of
melting point 137.degree. C.
Example 14
[0617] 88
[0618] 257 g (1.02 mmol) of the compound from Example No. I-1-a-62
together with 246 mg (1.2 mmol) of trimethyltin azide in toluene
are heated under reflux for 24 hours. After 24 hours, a further 120
mg of tin azide are added and the mixture is once more heated under
reflux for 5 hours. The tin adduct is subsequently filtered off
with suction. The starting material separates off on addition of 5
ml of 2 N NaOH solution, and is filtered off with suction. The pH
is adjusted to pH=1 using 2 N HCl and the prepared product is
filtered off with suction from the mixture which had been cooled to
0.degree. C.
[0619] This gave 0.06 g (yield 18% of theory) of solid
3-(4-tetrazolyl-phenyl)-3-oxo-2-piperidin-2-ylidene-propionitrile
of melting point greater than 220.degree. C.
Example 15
[0620] 89
[0621] 2.33 g (8.6 mmol) of the compound from Example No. I-1-a-63
are dissolved in 100 ml of ethanol (p.a.), and 300 mg of Raney.RTM.
nickel are added to the solution. Nitrogen is passed into the
reaction mixture for 5 minutes, followed by hydrogen at atmospheric
pressure for 8 hours. The mixture is subsequently again flushed
with nitrogen for 5 minutes. The Raney.RTM. nickel is filtered off,
and rinsed with 20 ml of ethanol and 50 ml of dichloromethane. The
combined filtrates are evaporated to dryness, and the residue is
dried under high vacuum.
[0622] This gave 2.03 g (yield 97.8% of theory) of solid
3-(4-nitrophenyl)-3-oxo-2-piperidin-2-ylidene-propionitrile of
melting point 182.degree. C.
Example 16
[0623] 90
[0624] Under protective gas, 0.4 g (1.66 mmol) of the compound from
Example No. I-1-a-137 in 5 ml of dichloromethane are initially
charged into an apparatus freed from moisture by heating, and the
mixture is cooled to -20.degree. C. At this temperature, 0.28 ml
(2.0 mmol) of triethylamine are added, and 0.33 ml (1.98 mmol) of
trifluoromethanesulphonic anhydride are then added dropwise. The
mixture is stirred at -20.degree. C. for 15 minutes. After warming
to 0.degree. C., stirring is continued for another 2 hours. To
bring the reaction to completion, a further 0.33 mmol of
trifluoromethanesulphonic anhydride are added at -20.degree. C.
After warming to 0.degree. C., the mixture is stirred for another
hour.
[0625] The reaction mixture is diluted with 50 ml of
dichloromethane and poured into 20 ml of 0.degree. C.-cold 1 N HCl.
The organic phase is separated off, dried over magnesium sulphate
and concentrated using a rotary evaporator. The reaction products
are separated by column chromatography on a silica phase using the
mobile phase ethyl acetate/cyclohexane 1:1.
[0626] This gives 316 mg (yield 51% of theory) of
3-[4-(trifluoromethanesu-
lphonylamino)-phenyl]-3-oxo-2-piperidin-2-ylidene-propionitrile of
melting point 197.degree. C.
Example 17
[0627] 91
[0628] 1.5 g (5,73 mmol) of the compound from Example No. I-2-a-2,
0.91 g (8.6 mmol) of methyl thioglycolate and 0.91 g of sodium
carbonate in 10 ml of anhydrous acetone are heated to 80.degree. C.
After 2 hours, a further 8.6 mmol of the methyl thioglycolate and
8.6 mmol of sodium methoxide are added, and the mixture is heated
under reflux for 24 hours. After cooling to room temperature, the
reaction mixture is poured into 150 ml of 1 M HCl. The reaction
product is filtered off as a solid residue and washed repeatedly
with 10 ml of methyl tert-butyl ether.
[0629] This gives 1.350 g of
3-[(2-methoxycarbonylmethylthio)-pyrid-5-yl]--
3-oxo-2-piperidin]-2-ylidene-propionitrile (yield 71% of theory) of
melting point 146.degree. C.
Example 18
[0630] 92
[0631] At 0.degree. C., 700 mg (2.1 mmol) of the compound from
Example No. I-2-a-6 are initially charged in 1.1 ml of a 1:1
mixture of 2 N NaOH and methanol. The mixture is subsequently
stirred at 0.degree. C. for 1 hour and at room temperature for a
further 4 hours. The resulting reaction solution is adjusted to pH
6 using 6 N HCl. The precipitated product is freed from moisture by
pressing on clay and dried under high vacuum.
[0632] This gives 551 mg (yield: 82.7% of theory) of
3-[4-(mercaptoacetic
acid)pyridyl]-3-oxo-2-pyridinyl-2-ylidene-propionitrile of melting
point 155.degree. C.
[0633] Analogously to the Preparation Examples 1 and 2, and in
accordance with the general statements about the preparation of
compounds of the formula (I-1-a), the following compounds are
obtained:
4TABLE 1 (I-1-a) 93 Comp.No. K T Y.sub.n Z m M.p. .degree. C.
I-1-a-2 O 4-OCH.sub.3 -- H 1 145 I-1-a-3 O 3,5-Cl.sub.2 -- H 1 124
I-1-a-4 O 4-t-C.sub.4H.sub.9 -- H 1 204-205 I-1-a-5 O 4-CH.sub.3 --
H 1 166-168 I-1-a-6 O 2,6-Cl.sub.2 -- H 1 196-198 I-1-a-7 O
2,4-Cl.sub.2 -- H 1 120 I-1-a-8 O 3,4-Cl.sub.2 -- H 1 179-180
I-1-a-9 O 2,5-Cl.sub.2 -- H 1 152 I-1-a-10 O 4-O-C.sub.6H.sub.5 --
H 1 136-138 I-1-a-11 O 4-CF.sub.3 -- H 1 138-140 I-1-a-12 O
4-OCF.sub.3 -- H 1 98 I-1-a-13 O 4-Br -- H 1 192 I-1-a-14 O
3,5-(CF.sub.3).sub.2 -- H 1 78 I-1-a-15 O 3-O-C.sub.6H.sub.5 -- H 1
178 I-1-a-16 O 2-NO.sub.2 -- H 1 206 I-1-a-17 O 3-NO.sub.2 -- H 1
223 I-1-a-18 O 3-Cl, 4-F -- H 1 176 I-1-a-19 O 4-Cl, 3-F -- H 1 178
I-1-a-20 O 4-CN -- H 1 215 I-1-a-21 O 4-NO.sub.2 -- H 1 221
I-1-a-22 O 3-Br -- H 1 193 I-1-a-23 O 2-S-CHF.sub.2 -- H 1 206
I-1-a-24 O 2,4-Cl.sub.2, 5-F -- H 1 175 I-1-a-25 O 3-CF.sub.3 -- H
1 119 I-1-a-26 O 3-Cl -- H 1 178 I-1-a-27 O 3,5-Cl.sub.2, 4-F -- H
1 203 I-1-a-28 O 4-Cl, 2-F -- H 1 182 I-1-a-29 O 3-CF.sub.3,
5-CH.sub.3 -- H 1 143 I-1-a-30 O 3-Cl, 4,5-F.sub.2 -- H 1 160
I-1-a-31 O 2-F -- H 1 168 I-1-a-32 O 3-F -- H 1 167 I-1-a-33 O
4-Cl, 3-CF.sub.3 -- H 1 156 I-1-a-34 O 4-CN, 2,5-F.sub.2 -- H 1 206
I-1-a-35 O 2,3-F.sub.2 -- H 1 185 I-1-a-36 O 4-CF.sub.3, 3-F -- H 1
185 I-1-a-37 O 3,4-O--CF.sub.2--O-- -- H 1 159 I-1-a-38 O
3,5-(CH.sub.3).sub.2 -- H 1 165 I-1-a-39 O 3,4,5-(OCH.sub.3).sub.3
-- H 1 159 I-1-a-40 O 2-Br, 4-OCH.sub.3 -- H 1 216 I-1-a-41 O
4-(4'-Cl--C.sub.6H.sub.4)-- -- H 1 131 I-1-a-42 O 2,4-Cl.sub.2 -- H
2 100 I-1-a-43 O 4-t-C.sub.4H.sub.9 -- H 2 169-170 I-1-a-44 O
4-CH.sub.3 -- H 2 165 I-1-a-45 O 3,4-Cl.sub.2 -- H 2 135 I-1-a-46 O
2,5-Cl.sub.2 -- H 2 102 I-1-a-47 O 4-OCH.sub.3 -- H 2 104 I-1-a-48
O 3,5-Cl.sub.2 -- H 2 90-92 I-1-a-49 O 2,6-Cl.sub.2 -- H 2 176-178
I-1-a-50 O 4-O--C.sub.6H.sub.5 -- H 2 128-130 I-1-a-51 O 4-CF.sub.3
-- H 2 126-128 I-1-a-52 O 4-OCF.sub.3 -- H 2 82-84 I-1-a-53 O 4-Br
-- H 2 149 I-1-a-54 O 4-(4'-Cl--C.sub.6H.sub.4)-- -- H 2 134
I-1-a-55 O 4-Cl -- H 2 149 I-1-a-56 O 3,5-(CF.sub.3).sub.2 -- H 2
64 I-1-a-57 O 2-NO.sub.2 -- H 2 222 I-1-a-58 O 3-O-C.sub.6H.sub.5
-- H 2 l I-1-a-59 O 3-NO.sub.2 -- H 2 194 I-1-a-60 O 3-Cl, 4-F -- H
2 148 I-1-a-61 O 4-Cl, 3-F -- H 2 167 I-1-a-62 O 4-CN -- H 2 196
I-1-a-63 O 4-NO.sub.2 -- H 2 217 I-1-a-64 O 3-Br -- H 2 107
I-1-a-65 O 2-S-CHF.sub.2 -- H 2 130 I-1-a-66 O 2,4-Cl.sub.2, 5-F --
H 2 132 I-1-a-67 O 3-CF.sub.3 -- H 2 129 I-1-a-68 O 3-Cl -- H 2 123
I-1-a-69 O 3-C.sub.6H.sub.5 -- H 2 188 I-1-a-70 O 3-(3'-Cl,
4'-F--C.sub.6H.sub.3)-- -- H 2 216 I-1-a-71 O
3-(4'-F--C.sub.6H.sub.4)-- -- H 2 234 I-1-a-72 O
3-(3'-NO.sub.2--C.sub.6H.sub.4)-- -- H 2 157 I-1-a-73 O
3,5-Cl.sub.2, 4-F -- H 2 150 I-1-a-74 O 4-Cl, 2-F -- H 2 177
I-1-a-75 O 3-CF.sub.3, 5-CH.sub.3 -- H 2 114 I-1-a-76 O 3-Cl,
4,5-F.sub.2 -- H 2 140 I-1-a-77 O 2-F -- H 2 154 I-1-a-78 O 3-F --
H 2 145 I-1-a-79 O 4-Cl, 3-CF.sub.3 -- H 2 141 I-1-a-80 O 4-CN,
2,5-F.sub.2 -- H 2 187 I-1-a-81 O 2,3-F.sub.2 -- H 2 210 I-1-a-82 O
4-CF.sub.3, 3-F -- H 2 160 I-1-a-83 O 3,4-O--CF.sub.2--O-- -- H 2
163 I-1-a-84 O 3,5-Br.sub.2 -- H 2 118 I-1-a-85 O
3,5-(CH.sub.3).sub.2 -- H 2 133 I-1-a-86 O 3,4,5-(OCH.sub.3).sub.3
-- H 2 139 I-1-a-87 O 3,5-(OC.sub.2H.sub.5).sub.2 -- H 2 105
I-1-a-88 O 3-Br, 4-OCH.sub.3 -- H 2 171 I-1-a-89 O 4-Cl -- H 3 158
I-1-a-90 O 4-CH.sub.3 -- H 3 124 I-1-a-91 O 4-OCH.sub.3 -- H 3 82
I-1-a-92 O 3-Cl -- H 3 136 I-1-a-93 O 2,4-Cl.sub.2 -- H 3 167
I-1-a-94 O 3,5-(CF.sub.3).sub.2 -- H 3 129 I-1-a-95 O 3-Br H 3 137
I-1-a-96 O 3-NO.sub.2 -- H 3 127 I-1-a-97 O 3-O--C.sub.6H.sub.5 --
H 3 103 I-1-a-98 O 3-CF.sub.3 -- H 3 145 I-1-a-99 O 4-Cl, 3-F -- H
3 143 I-1-a-100 O 3-Cl, 4-F -- H 3 145 I-1-a-101 O 3-Cl -- H 3 139
I-1-a-102 O 4-CN, 2,5-F.sub.2 -- H 3 192 I-1-a-103 O 2,4,5-F.sub.3
-- H 1 174 I-1-a-104 O 3-NO.sub.2, 5-CF.sub.3 -- H 1 152 I-1-a-105
O 4-Cl, 2,5-F.sub.2 -- H 1 162 I-1-a-106 O
3,4,5-(OC.sub.2H.sub.5).sub.3 -- H 1 166 I-1-a-107 O 2,4-F.sub.2 --
H 1 180 I-1-a-108 O 4-CO.sub.2CH.sub.3 -- H 1 207 I-1-a-109 O
4-CO.sub.2H -- H 1 >220 1-1-a-110 O 4-Cl -- CH.sub.3 1 115
I-1-a-111 O 2,5-F.sub.2, 4-CN -- CH.sub.3 1 158 I-1-a-112 O 2-F,
4-Br -- H 1 195 I-1-a-113 O 2,6-Cl.sub.2, 4-CF.sub.3 -- H 1 114
I-1-a-114 O 2-F, 4-NO.sub.2 -- H 1 176 I-1-a-115 O 2-F, 4-CF.sub.3
-- H 1 169 I-1-a-116 O 2-CF.sub.3 -- H 1 148 I-1-a-117 O
3,4-O--(CF.sub.2).sub.2--O-- -- H 1 109 I-1-a-118 O
2,3-O--CF.sub.2--O-- -- H 1 147 I-1-a-119 O 2-Cl, 4-SCH.sub.3 -- H
1 174 I-1-a-120 O 2,4-Cl.sub.2, 5-NO.sub.2 -- H 1 190 I-1-a-121 O
2,6-F.sub.2 -- H 1 184 I-1-a-122 O 2-Cl, 3-CF.sub.3 -- H 1 206
I-1-a-123 O 4-OCF.sub.3, 3-NO.sub.2 -- H 1 113 I-1-a-124 O
2-NO.sub.2, 4-Cl -- H 1 184 I-1-a-125 O 4-Cl 3,3-(CH.sub.3).sub.2 H
1 141 I-1-a-126 O 4-Cl 5,6-CH.dbd.CH--CH.dbd.CH-- H 2 196 I-1-a-127
O 2,5-F.sub.2, 4-CN 5,6-CH.dbd.CH--CH.dbd.CH-- H 2 215 I-1-a-128 O
3,5-(CF.sub.3)2 5,6-CH.dbd.CH--CH.dbd.CH-- H 2 167 I-1-a-129 O
2,4,5-F.sub.3 -- H 2 189 I-1-a-130 O 3-NO.sub.2, 5-CF.sub.3 -- H 2
138 I-1-a-131 O 4-Cl, 2,5-F.sub.2 -- H 2 186 I-1-a-132 O
3,4,5-(OC.sub.2H.sub.5).sub.3 -- H 2 155 I-1-a-133 O 2,4-F.sub.2 --
H 2 168 I-1-a-134 O 4-CO.sub.2CH.sub.3 -- H 2 179 I-1-a-135 O
4-CO.sub.2H -- H 2 >220 I-1-a-136 O 4-Br, 2-F -- H 2 175
I-1-a-137 O 4-NH.sub.2 -- H 2 182 I-1-a-138 O 4-NH SO.sub.2CF.sub.3
-- H 2 197 I-1-a-139 O 2-CF.sub.3 -- H 2 153 I-1-a-140 O
2,6-Cl.sub.2, 4-CF.sub.3 -- H 2 164 I-1-a-141 O 2-F, 4-NO.sub.2 --
H 2 192 I-1-a-142 O 2-F, 4-CF.sub.3 -- H 2 180 I-1-a-143 O
4-SCH.sub.3, 2-Cl -- H 2 128 I-1-a-144 O 2,4-Cl.sub.2, 5-NO.sub.2
-- H 2 204 I-1-a-145 O 4-Cl, 2-F, 5-NO.sub.2 -- H 2 177 I-1-a-146 O
4-OCF.sub.3, 3-NO.sub.2 -- H 2 113 I-1-a-147 O 4-OCF.sub.3,
3-NH.sub.2 -- H 2 141 I-1-a-148 O 4-Br, 2-F, 5-NH.sub.2 -- H 2 148
I-1-a-149 O 4-Cl -- CH.sub.3 2 110 I-1-a-150 O 94 -- H 2 >220
I-1-a-151 S 4-Cl -- H 2 137 I-1-a-152 O
4-(2-CH'.sub.3--C.sub.6H.sub.4) -- H 2 199 I-1-a-153 O
4-(3,5-(CF.sub.3)'--C.sub.6H.sub.3) -- H 2 220 I-1-a-154 O
4-NHSO.sub.2--CH.sub.3 -- H 2 210 I-1-a-155 O 95 -- H 2 >220
I-1-a-156 O 2,4-F.sub.2, 5-NO.sub.2 -- H 2 207 I-1-a-157 O
2,6-F.sub.2 -- H 2 195 I-1-a-158 O 2-F, 3-CF.sub.3 -- H 2 189
I-1-a-159 O 2-Cl, 6-F -- H 2 I-1-a-160 O 2-Cl, 3-CF.sub.3 -- H 2
171 I-1-a-161 S 4-Cl -- CH.sub.3 1 172 I-1-a-162 O
3-O-(3-Cl'--C.sub.6H.sub.4), 5-NO.sub.2 -- H 1 161 I-1-a-163 O
3-O-(3-Cl'--C.sub.6H.sub.4), 5-NO.sub.2 -- H 2 94
[0634] Analogously to Preparation Example 1, and in accordance with
the general statements about the preparation, the following
compounds of the formula I-2-a are obtained:
5TABLE 2 (I-2-a) 96 Comp.No. T Y.sub.n m M.p. .degree. C. I-2-a-1
2-Cl -- 1 156--158 I-2-a-2 2-Cl -- 2 258--260 I-2-a-3 2,6-Cl.sub.2,
4-CH.sub.3 -- 1 >220 I-2-a-4 6-Cl -- 1 30 I-2-a-5 2-Cl
5,6-CH.dbd.CH--CH.dbd.CH-- 2 183 I-2-a-6
2-S-CH.sub.2--CO.sub.2--CH.sub.3-- -- 2 146 I-2-a-7
2-S-CH.sub.2--CO.sub.2--H -- 2 155 I-2-a-8 2,6-Cl.sub.2 -- 2 121
I-2-a-9 2,6-Cl.sub.2, 4-CH.sub.3 -- 2 176 I-2-a-10
2-S-4-[(4'-C.sub.6H.sub.5)--C.sub.6H.sub.4] -- 2 197 I-2-a-11 6-Cl
-- 2 179
[0635] Analogously to Preparation Example 1, and in accordance with
the general statements about the preparation, the following
compounds of the formula I-3-a are obtained:
6TABLE 3 (I-3-a) 97 Comp. N. T m M.p. .degree. C. I-3-a-1 2-Br 1
201 I-3-a-2 3-Br 1 198 I-3-a-3 2-Cl 2 141 I-3-a-4 2-Br 2 159
I-3-a-5 3-Br 2 215 I-3-a-6 3-Br 3 162 I-3-a-7 2-Cl 3 176 I-3-a-8
2-Br 3 163 I-3-a-9 3-(4-Cl'--C.sub.6H.sub.4), 2-CF.sub.3 1 176
I-3-a-10 2,3-(CH.dbd.CH--CCl.dbd.CH)-- 1 198 I-3-a-11
2-(4-Cl'--C.sub.6H.sub.4) 2 207 I-3-a-12 3-(4-Cl'--C.sub.6H.sub.4),
2-CF.sub.3 2 170 I-3-a-13 2-(3-Cl', 4-F'--C.sub.6H.sub.3) 2 175
I-3-a-14 2-(3,5-(CF.sub.3)'.sub.2--C.s- ub.6H.sub.3) 2 >223
I-3-a-15 2-(4-F'--C.sub.6H.sub.4) 2 195 I-3-a-16
2-(3-NO.sub.2'--C.sub.6H.sub.4) 2 202
[0636] Analogously to Preparation Example 1, and in accordance with
the general statements about the preparation, the following
compounds of the formula I-4-a are obtained:
7TABLE 4 (I-4-a) 98 Comp. No. K T Y.sub.n m M.p. .degree. C.
I-4-a-1 O 7-Cl -- 1 >220 I-4-a-2 O 7-Cl -- 2 >220
[0637] Analogously to Preparation Example 1, and in accordance with
the general statements about the preparation, the following
compounds of the formula I-5-a are obtained:
8TABLE 5 (I-5-a) Comp. No. K T Y.sub.n m M.p. .degree. C. I-5-a-1 O
2-SCH.sub.3, 5-Br -- 1 170 I-5-a-2 O 2-SCH.sub.3, 5-Br -- 2 180
[0638] Analogously to Preparation Example 1, and in accordance with
the general statements about the preparation, the following
compounds of the formula I-6-a are obtained:
9TABLE 6 (I-6-a) 99 Comp. No. K T Y.sub.n m M.p. .degree. C.
I-6-a-1 O H -- 1 199 I-6-a-2 O H -- 2
[0639] Analogously to Preparation Example 3, and in accordance with
the general statements about the preparation, the following
compounds of the formula I-1-b are obtained:
10TABLE 7 (I-1-b) 100 Comp. No. T m Z M.p. .degree. C. I-1-b-3 4-Cl
1 101 118-120 I-1-b-4 3,4-Cl.sub.2 1 102 68-70 I-1-b-5 4-Cl 2 103
136-138 I-1-b-6 2-Cl 2 104 204-205 I-1-b-7 2-Cl 1 105 100-101
[0640] Analogously to Preparation Example 7, the compound I-1-d-4
of m.p. 222-224.degree. C. is obtained. 106
[0641] Analogously to Preparation Example 3, the compound I-1-d-5
of m.p. 140-142.degree. C. is obtained. 107
Example
[0642]
11 Phaedou larvae test Solvent: 7 parts by weight of
dimethylformamide Emulsifier: 1 part by weight of alkylaryl
polyglycol ether
[0643] To produce a suitable preparation of active compound, 1 part
by weight of active compound is mixed with the stated amounts of
solvent and emulsifier, and the concentrate is diluted with water
to the desired concentration.
[0644] Cabbage leaves (Brassica oleracea) are treated by being
dipped into the preparation of active compound of the desired
concentration and are populated with larvae of the mustard beetle
(Phaedon cochleariae) while the leaves are still moist.
[0645] After the desired period of time, the kill in % is
determined. 100% means that all beetle larvae have been killed; 0%
means that none of the beetle larvae have been killed.
[0646] In this test, for example, the following compounds of the
Preparation Examples show good activity: I-1-a-I 1, I-1-a-12,
I-1-a-52.
Example
[0647]
12 Spodoptera frugiperda test Solvent: 7 parts by weight of
dimethylformamide Emulsifier:: 1 part by weight of alkylaryl
polyglycol ether
[0648] To produce a suitable preparation of active compound, 1 part
by weight of active compound is mixed with the stated amounts of
solvent and emulsifier, and the concentrate is diluted with water
to the desired concentration.
[0649] Cabbage leaves (Brassica oleracea) are treated by being
dipped into the preparation of active compound of the desired
concentration and are populated with caterpillars of the army worm
(Spodoptera frugiperda) while the leaves are still moist.
[0650] After the desired period of time, the kill in % is
determined. 100% means that all caterpillars have been killed; 0%
means that none of the caterpillars have been killed.
[0651] In this test, for example, the following compounds of the
Preparation Examples show good activity: I-2-a-2, compound
according to Preparation Example 3.
Example
[0652]
13 Tetranychus test (OP-resistant/dip treatment) Solvent: 7 parts
by weight of dimethylformamide Emulsifier: 1 part by weight of
alkylaryl polyglycol ether
[0653] To produce a suitable preparation of active compound, 1 part
by weight of active compound is mixed with the stated amounts of
solvent and emulsifier, and the concentrate is diluted with water
to the desired concentration.
[0654] Bean plants (Phaseolus vulgaris) which are heavily infested
by all stages of the greenhouse red spider mite (Tetranychus
urticae) are dipped into the preparation of active compound of the
desired concentration.
[0655] After the desired period of time, the kill in % is
determined. 100% means that all spider mites have been killed; 0%
means that none of the spider mites have been killed.
[0656] In this test, for example, the following compounds of the
Preparation Examples show good activity: I-1-a-7, I-1-a-48,
I-1-a-56.
Example
[0657]
14 Post emergence test Solvent: 5 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
[0658] 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.
[0659] Test plants which have a height of 5 to 15 cm are sprayed
with the preparation of active compound such that the particular
desired amounts of active compound are applied per unit area. After
3 weeks, the degree of damage to the plants is assessed in % damage
in comparison to the development of the untreated controls.
[0660] The figures denote:
[0661] 0% no effect (like untreated control)
[0662] 100% =total destruction
[0663] In this test, for example, the compounds of Preparation
Example I-1-a-9, I-1-a-14, I-1-a-20, I-1-a-54, I-1-a-55, I-1-a-62,
I-2-a-2 show strong activity against weeds, and some of them are
tolerated well by crop plants, such as, for example, wheat.
Example
[0664]
15 Pre-emergence test Solvent: 5 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
[0665] 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.
[0666] Seeds of the test plants are sown in normal soil and, after
24 hours, watered with the preparation of active compound. The
amount of water per unit area is advantageously kept constant. The
concentration of active compound in the preparation is immaterial,
only the active compound application rate per unit area matters.
After three weeks, the degree of damage to the plants is assessed
in % damage in comparison with the development of the untreated
control.
[0667] The figures denote:
[0668] 0% no effect (like untreated control)
[0669] 100% =total destruction
[0670] In this test, for example, the compounds of Preparation
Example I-1-a-14, -1-a-46, I-1-a-51, I-1-a-52, I-1-a-53, I-1-a-54,
I-1-a-55, I-1-a-62, I-1-a-66, I-2-a-2 show strong activity against
weeds, and some of them are tolerated well by crop plants, such as,
for example, wheat and soya.
* * * * *