U.S. patent application number 10/898819 was filed with the patent office on 2005-01-13 for substituted aryl ketones.
Invention is credited to Dahmen, Peter, Drewes, Mark Wilhelm, Feucht, Dieter, Goto, Toshio, Hoischen, Dorothee, Lehr, Stefan, Muller, Klaus-Helmut, Narabu, Shinichi, Pontzen, Rolf, Schallner, Otto, Schwarz, Hans-Georg, Yanagi, Akihiko.
Application Number | 20050009704 10/898819 |
Document ID | / |
Family ID | 26003876 |
Filed Date | 2005-01-13 |
United States Patent
Application |
20050009704 |
Kind Code |
A1 |
Schallner, Otto ; et
al. |
January 13, 2005 |
Substituted aryl ketones
Abstract
The invention relates to novel substituted aryl ketones of the
general formula (I) 1 in which n represents the number 0, 1 or 2, A
represents alkanediyl (alkylene), R.sup.1 represents one of the
groupings below 2 where m, R.sup.5, R.sup.6, R.sup.7, R.sup.8,
R.sup.9, R.sup.10, R.sup.11, R.sup.12 and R.sup.13 each have one of
the meanings given in the description, R.sup.2 represents hydrogen,
nitro, cyano, carboxyl, carbamoyl, thiocarbamoyl, halogen, or
represents in each case optionally substituted alkyl, alkoxy,
alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino, dialkylamino
or dialkylaminosulphenyl, R.sup.3 represents nitro, cyano,
carboxyl, carbamoyl, thiocarbamoyl, halogen, or represents in each
case optionally substituted alkyl, alkoxy, alkylthio,
alkyl-sulphinyl, alkylsulphonyl, alkylamino, dialkylamino or
dialkylaminosulphonyl, and R.sup.4 represents an optionally
substituted 4- to 12-membered, saturated or unsaturated, monocyclic
or bicyclic heterocyclic grouping, and to processes for their
preparation, to intermediates and to the use of these compounds as
herbicides.
Inventors: |
Schallner, Otto; (Monheim,
DE) ; Lehr, Stefan; (Langenfeld, DE) ;
Schwarz, Hans-Georg; (Langenfeld, DE) ; Muller,
Klaus-Helmut; (Dusseldorf, DE) ; Hoischen,
Dorothee; (Dusseldorf, DE) ; Drewes, Mark
Wilhelm; (Langendfeld, DE) ; Dahmen, Peter;
(Neuss, DE) ; Feucht, Dieter; (Monheim, DE)
; Pontzen, Rolf; (Leichlingen, DE) ; Yanagi,
Akihiko; (Tochigi, JP) ; Narabu, Shinichi;
(Ibaraki, JP) ; Goto, Toshio; (Tochigi,
JP) |
Correspondence
Address: |
BAYER CROPSCIENCE LP
Patent Department
100 BAYER ROAD
PITTSBURGH
PA
15205-9741
US
|
Family ID: |
26003876 |
Appl. No.: |
10/898819 |
Filed: |
July 26, 2004 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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10898819 |
Jul 26, 2004 |
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10181327 |
Jul 15, 2002 |
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10181327 |
Jul 15, 2002 |
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PCT/EP01/00092 |
Jan 5, 2001 |
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Current U.S.
Class: |
504/271 ;
504/280; 504/348; 548/248; 548/374.1 |
Current CPC
Class: |
C07D 207/26 20130101;
C07D 249/12 20130101; A01N 43/653 20130101; C07D 403/12 20130101;
C07D 257/04 20130101; C07D 213/64 20130101; A01N 43/40
20130101 |
Class at
Publication: |
504/271 ;
504/280; 504/348; 548/248; 548/374.1 |
International
Class: |
A01N 043/00; A01N
043/80; A01N 043/56; A01N 035/00 |
Foreign Application Data
Date |
Code |
Application Number |
Jan 17, 2000 |
DE |
100 01 588.3 |
Aug 14, 2000 |
DE |
100 39 723.9 |
Claims
1-12. (Cancelled).
12. A substituted aryl ketone of the formula (I) 226wherein n
represents the number 0, 1 or 2, A represents alkanediyl
(alkylene), R.sup.1 represents one of the groupings below 227where
m represents the numbers 0 to 6, R.sup.5 represents halogen or
represents in each case optionally substituted alkyl, alkylthio or
aryl or--if m represents 2--optionally also together with a second
radical R.sup.5 represents alkanediyl (alkylene), R.sup.6
represents hydroxyl, formyloxy, halogen, or represents in each case
optionally substituted alkoxy, alkylthio, alkylsulphinyl,
alkylsulphonyl, alkylcarbonyloxy, alkoxycarbonyloxy,
alkylaminocarbonyloxy, alkylsulphonyloxy, alkenyloxy, alkinyloxy,
aryloxy, arylthio, arylsulphinyl, arylsulphonyl, arylcarbonyloxy,
arylcarbonylalkoxy, arylsulphonyloxy, arylalkoxy, arylalkylthio,
arylalkylsulphinyl or arylalkylsulphonyl, R.sup.10 represents
hydrogen, cyano, carbamoyl, thiocarbamoyl, halogen, or represents
in each case optionally substituted alkyl, alkylcarbonyl, alkoxy,
alkoxycarbonyl, alkylthio, alkylsulphinyl or alkylsulphonyl,
R.sup.11 represents hydrogen or represents in each case optionally
substituted alkyl or cycloalkyl, R.sup.12 represents hydrogen or
represents in each case optionally substituted alkyl or cycloalkyl,
and R.sup.13 represents hydrogen, cyano, carbamoyl, halogen, or
represents in each case optionally substituted alkyl, alkoxy,
alkoxycarbonyl, alkylthio, alkylsulphinyl or alkylsulphonyl,
R.sup.2 represents hydrogen, nitro, cyano, carboxyl, carbamoyl,
thiocarbamoyl, halogen, or represents in each case optionally
substituted alkyl, alkoxy, alkylthio, alkylsulphinyl,
alkylsulphonyl, alkylamino, dialkylamino or dialkylaminosulphonyl,
R.sup.3 represents nitro, cyano, carboxyl, carbamoyl,
thiocarbamoyl, halogen, or represents in each case optionally
substituted alkyl, alkoxy, alkylthio, alkylsulphinyl,
alkylsulphonyl, alkylamino, dialkylamino or dialkylaminosulphonyl,
and R.sup.4 represents an optionally substituted 4- to 12-membered,
saturated or unsaturated, monocyclic or bicyclic heterocyclic
grouping which contains 1 to 4 hetero atoms (up to 4 nitrogen atoms
and optionally--alternatively, or additionally--one or two oxygen
atoms or one or two sulphur atoms, or one or two SO groupings or
one or two SO.sub.2 groupings), and which additionally contains one
to three oxo groups (C.dbd.O) and/or thioxo groups (C.dbd.S) as
components of the heterocycle, including all possible tautomeric
forms of the compounds of the formula (I) and the possible salts
and acid or base adducts of the compounds of the formula (I).
13. A compound of the formula (I) according to claim 12, wherein n
represents the number 0 or 1, m represents the number 0, 1, 2, 3 or
4, A represents alkanediyl (alkylene) having 1 to 6 carbon atoms,
R.sup.1 represents one of the groupings below 228R.sup.2 represents
hydrogen, nitro, cyano, carboxyl, carbamoyl, thiocarbamoyl,
halogen, or represents in each case optionally cyano-, halogen-,
C.sub.1-C.sub.4-alkoxy-, C.sub.1-C.sub.4-alkylthio-,
C.sub.1-C.sub.4-alkylsulphinyl- or
C.sub.1-C.sub.4-alkylsulphonyl-substituted alkyl, alkoxy,
alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino, dialkylamino
or dialkylaminosulphonyl having in each case 1 to 6 carbon atoms in
the alkyl groups, R.sup.3 represents nitro, cyano, carboxyl,
carbamoyl, thiocarbamoyl, halogen, or represents in each case
optionally cyano-, halogen-, C.sub.1-C.sub.4-alkoxy-,
C.sub.1-C.sub.4-alkylthio-, C.sub.1-C.sub.4-alkylsulphinyl- or
C.sub.1-C.sub.4-alkylsulphonyl-substit- uted alkyl, alkoxy,
alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino, dialkylamino
or dialkylaminosulphonyl having in each case 1 to 6 carbon atoms in
the alkyl groups, R.sup.4 represents one of the heterocyclic
groupings below 229230where in each case the broken bond is a
single bond or a double bond, Q represents oxygen or sulphur,
R.sup.14 represents hydrogen, hydroxyl, mercapto, cyano, halogen,
represents in each case optionally cyano-, halogen-,
C.sub.1-C.sub.4-alkoxy-, C.sub.1-C.sub.4-alkylthio-,
C.sub.1-C.sub.4-alkylsulphinyl- or
C.sub.1-C.sub.4-alkylsulphonyl-substituted alkyl, alkylcarbonyl,
alkoxy, alkoxycarbonyl, alkylthio, alkylsulphinyl or alkylsulphonyl
having in each case up to 6 carbon atoms in the alkyl groups,
represents in each case optionally halogen-substituted alkylamino
or dialkylamino having in each case up to 6 carbon atoms in the
alkyl groups, represents in each case optionally
halogen-substituted alkenyl, alkinyl, alkenyloxy, alkenylthio or
alkenylamino having in each case up to 6 carbon atoms in the
alkenyl or alkinyl groups, represents in each case optionally
halogen-substituted cycloalkyl, cycloalkyloxy, cycloalkylthio,
cycloalkylamino, cycloalkylalkyl, cycloalkylalkoxy,
cycloalkylalkylthio or cycloalkylalkylamino having in each case 3
to 6 carbon atoms in the cycloalkyl groups and optionally up to 4
carbon atoms in the alkyl moiety, or represents in each case
optionally halogen-, C.sub.1-C.sub.4-alkyl- or
C.sub.1-C.sub.4-alkoxy-substituted phenyl, phenyloxy, phenylthio,
phenylamino, benzyl, benzyloxy, benzylthio or benzylamino,
represents pyrrolidino, piperidino or morpholino, or--if two
adjacent radicals R.sup.14 and R.sup.14 are located at a double
bond--also together with the adjacent radical R.sup.14 represents a
benzo grouping, and R.sup.15 represents hydrogen, hydroxyl, amino,
alkylideneamino having up to 4 carbon atoms, represents in each
case optionally halogen- or C.sub.1-C.sub.4-alkoxy-substituted
alkyl, alkoxy, alkylamino, dialkylamino or alkaneoylamino having in
each case up to 6 carbon atoms in the alkyl groups, represents in
each case optionally halogen-substituted alkenyl, alkinyl or
alkenyloxy having in each case up to 6 carbon atoms in the alkenyl
or alkinyl groups, represents in each case optionally
halogen-substituted cycloalkyl, cycloalkylalkyl or cycloalkylamino
having in each case 3 to 6 carbon atoms in the cycloalkyl groups
and optionally up to 3 carbon atoms in the alkyl moiety, or
represents in each case optionally halogen-, C.sub.1-C.sub.4-alkyl-
or C.sub.1-C.sub.4-alkoxy-substituted phenyl or benzyl, or together
with an adjacent radical R.sup.14 or R.sup.15 represents optionally
halogen- or C.sub.1-C.sub.4-alkyl-substituted alkanediyl having 3
to 5 carbon atoms, where the individual radicals R.sup.14 and
R.sup.15--if more than one of them are attached to the same
heterocyclic groupings--can have identical or different meanings
within the scope of the above definition, R.sup.5 represents
halogen, represents in each case optionally cyano-, halogen- or
C.sub.1-C.sub.4-alkoxy-substituted alkyl or alkylthio having in
each case 1 to 6 carbon atoms, represents optionally halogen-,
C.sub.1-C.sub.4-alkyl- or C.sub.1-C.sub.4-alkoxy-substituted
phenyl, or optionally also--if m represents 2--together with a
second radical R.sup.5 represents alkanediyl having 2 to 6 carbon
atoms, R.sup.6 represents hydroxyl, formyloxy, or represents in
each case optionally cyano-, halogen- or
C.sub.1-C.sub.4-alkoxy-substituted alkoxy, alkylthio,
alkylsulphinyl, alkylsulphonyl, alkylcarbonyloxy,
alkoxycarbonyloxy, alkylaminocarbonyloxy or alkylsulphonyloxy
having in each case 1 to 6 carbon atoms in the alkyl groups,
represents in each case optionally cyano- or halogen-substituted
alkenyloxy or alkinyloxy having in each case 2 to 6 carbon atoms,
or represents in each case optionally nitro-, cyano-, halogen-,
C.sub.1-C.sub.4-alkyl-, C.sub.1-C.sub.4-halogenoalkyl-,
C.sub.1-C.sub.4-alkoxy- or
C.sub.1-C.sub.4-halogenoalkoxy-substituted aryloxy, arylthio,
arylsulphinyl, arylsulphonyl, arylcarbonyloxy, arylcarbonylalkoxy,
arylsulphonyloxy, arylalkoxy, arylalkylthio, arylalkylsulphinyl or
arylalkylsulphonyl having in each case 6 or 10 carbon atoms in the
aryl group and optionally 1 to 4 carbon atoms in the alkyl moiety,
R.sup.10 represents hydrogen, cyano, carbamoyl, thiocarbamoyl,
halogen, or represents in each case optionally cyano-, halogen- or
C.sub.1-C.sub.4-alkoxy-substituted alkyl, alkylcarbonyl, alkoxy,
alkoxycarbonyl, alkylthio, alkylsulphinyl or alkylsulphonyl having
in each case 1 to 6 carbon atoms in the alkyl groups, R.sup.11
represents hydrogen, represents optionally cyano-, halogen- or
C.sub.1-C.sub.4-alkoxy-substituted alkyl having 1 to 6 carbon atoms
or represents optionally cyano-, halogen- or
C.sub.1-C.sub.4-alkyl-substitut- ed cycloalkyl having 3 to 6 carbon
atoms, R.sup.12 represents hydrogen, represents optionally cyano-,
halogen- or C.sub.1-C.sub.4-alkoxy-substitu- ted alkyl having 1 to
6 carbon atoms or represents optionally cyano-, halogen- or
C.sub.1-C.sub.4-alkyl-substituted cycloalkyl having 3 to 6 carbon
atoms, and R.sup.13 represents hydrogen, cyano, carbamoyl, halogen,
or represents in each case optionally cyano-, halogen- or
C.sub.1-C.sub.4-alkoxy-substituted alkyl, alkoxy, alkoxycarbonyl,
alkylthio, alkylsulphinyl or alkylsulphonyl having in each case 1
to 6 carbon atoms in the alkyl groups.
14. A compound of the formula (I) according to claim 12 wherein m
represents the numbers 0, 1, 2 or 3, A represents methylene,
ethane-1,2-diyl(dimethylene), ethane-1,1-diyl, propane-1,2-diyl,
propane-1,3-diyl(trimethylene), butane-1,2-diyl, butane-1,3-diyl or
butane-1,4-diyl(tetramethylene), R.sup.2 represents hydrogen,
nitro, cyano, carboxyl, carbamoyl, thiocarbamoyl, fluorine,
chlorine, bromine, iodine, or represents in each case optionally
fluorine- and/or chlorine-, methoxy-, ethoxy-, n- or i-propoxy-,
methylthio-, ethylthio-, n- or i-propylthio-, methylsulphinyl-,
ethylsulphinyl-, methylsulphonyl- or ethylsulphonyl-substituted
methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, represents in
each case optionally fluorine- and/or chlorine-, methoxy- ethoxy-,
n- or i-propoxy-substituted methoxy, ethoxy, n- or i-propoxy,
represents in each case optionally fluorine- and/or
chlorine-substituted methylthio, ethylthio, n- or i-propylthio,
methylsulphinyl, ethylsulphinyl, n- or i-propylsulphinyl,
methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl, or
represents methylamino, ethylamino, n- or i-propylamino,
dimethylamino, diethylamino, dimethylaminosulphonyl or
diethylaminosulphonyl, R.sup.3 represents nitro, cyano, carboxyl,
carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine, represents
in each case optionally fluorine- and/or chlorine-, methoxy-,
ethoxy-, n- or i-propoxy-, methylthio-, ethylthio-, n- or
i-propylthio-, methylsulphinyl-, ethylsulphinyl-, methylsulphonyl-
or ethylsulphonyl-substituted methyl, ethyl, n- or i-propyl, n-,
i-, s- or t-butyl, represents in each case optionally fluorine-
and/or chlorine-, methoxy-, ethoxy-, n- or i-propoxy-substituted
methoxy, ethoxy, n- or i-propoxy, represents in each case
optionally fluorine- and/or chlorine-substituted methylthio,
ethylthio, n- or i-propylthio, methylsulphinyl, ethylsulphinyl, n-
or i-propylsulphinyl, methylsulphonyl, ethylsulphonyl, n- or
i-propylsulphonyl, or represents methylamino, ethylamino, n- or
i-propylamino, dimethylamino, diethylamino, dimethylaminosulphonyl
or diethylaminosulphonyl, R.sup.4 represents one of the
heterocyclic groupings below, 231R.sup.5 represents fluorine,
chlorine, bromine, represents in each case optionally cyano-,
fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl,
n- or i-propyl, n-, i-, s- or t-butyl, methylthio, ethylthio, n- or
i-propylthio, n-, i-, s- or t-butylthio, represents optionally
fluorine-, chlorine-, methyl- or methoxy-substituted phenyl, or
optionally also--if m represents 2--together with a second radical
R.sup.5 represents ethane-1,2-diyl(dimethylene),
propane-1,3-diyl(trimeth- ylene) or
butane-1,4-diyl(tetramethylene), R.sup.6 represents hydroxyl,
formyloxy, represents in each case optionally cyano-, fluorine-,
chlorine-, methoxy- or ethoxy-substituted methoxy, ethoxy, n- or
i-propoxy, n-, i-, s- or t-butoxy, methylthio, ethylthio, n- or
i-propylthio, n-, i-, s- or t-butylthio, methylsulphinyl,
ethylsulphinyl, n- or i-propylsulphinyl, methylsulphonyl,
ethylsulphonyl, n- or i-propylsulphonyl, acetyloxy, propionyloxy,
n- or i-butyroyloxy, methoxycarbonyloxy, ethoxycarbonyloxy, n- or
i-propoxycarbonyloxy, methylaminocarbonyloxy,
ethylaminocarbonyloxy, n- or i-propylaminocarbonyloxy,
methylsulphonyloxy, ethylsulphonyloxy, n- or i-propylsulphonyloxy,
represents in each case optionally cyano-, fluorine-, chlorine- or
bromine-substituted propenyloxy, butenyloxy, propinyloxy or
butinyloxy, or represents in each case optionally nitro-, cyano-,
fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-,
n-, i-, s- or t-butyl-, trifluoromethyl-, methoxy-, ethoxy-, n- or
i-propoxy-, n-, i-, s- or t-butoxy-, difluoromethoxy- or
trifluoromethoxy-substituted phenoxy, phenylthio, phenylsulphinyl,
phenylsulphonyl, benzoyloxy, benzoylmethoxy, phenylsulphonyloxy,
phenylmethoxy, phenylmethylthio, phenylmethylsulphinyl or
phenylmethylsulphonyl, R.sup.10 represents hydrogen, cyano,
carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine, or
represents in each case optionally cyano-, fluorine-, chlorine-,
bromine-, methoxy-, ethoxy-, n- or i-propoxy-substituted methyl,
ethyl, n- or i-propyl, n-, i-, s- or t-butyl, acetyl, propionyl, n-
or i-butyroyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or
t-butoxy, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl,
methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or
t-butylthio, methylsulphinyl, ethylsulphinyl, n- or
i-propylsulphinyl, methylsulphonyl, ethylsulphonyl, n- or
i-propylsulphonyl, R.sup.11 represents hydrogen, represents in each
case optionally cyano-, fluorine-, chlorine-, bromine-, methoxy- or
ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or
t-butyl, or represents in each case optionally cyano-, fluorine-,
chlorine-, bromine-, methyl- or ethyl-substituted cyclopropyl,
cyclobutyl, cyclopentyl or cyclohexyl, R.sup.12 represents
hydrogen, represents in each case optionally cyano-, fluorine-,
chlorine-, bromine-, methoxy- or ethoxy-substituted methyl, ethyl,
n- or i-propyl, n-, i-, s- or t-butyl, or represents in each case
optionally cyano-, fluorine-, chlorine-, bromine-, methyl- or
ethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl or
cyclohexyl, R.sup.13 represents hydrogen, cyano, carbamoyl,
fluorine, chlorine, bromine, or represents in each case optionally
cyano-, fluorine-, chlorine-, bromine-, methoxy- or
ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or
t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy,
methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl,
methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or
t-butylthio, methylsulphinyl, ethylsulphinyl, n- or
i-propylsulphinyl, methylsulphonyl, ethylsulphonyl, n- or
i-propylsulphonyl, R.sup.14 represents hydrogen, hydroxyl,
mercapto, cyano, fluorine, chlorine, bromine, iodine, represents in
each case optionally fluorine-, chlorine-, methoxy-, ethoxy-, n- or
i-propoxy-, n-, i-, s- or t-butoxy-, methylthio-, ethylthio-, n- or
i-propylthio-, n-, i-, s- or t-butylthio-, methylsulphinyl-,
ethylsulphinyl-, n- or i-propylsulphinyl-, methylsulphonyl-,
ethylsulphonyl-, n- or i-propylsulphonyl-substituted methyl, ethyl,
n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or
i-propoxy, n-, i-, s- or t-butoxy, methylthio, ethylthio, n- or
i-propylthio, n-, i-, s- or t-butylthio, methylsulphinyl,
ethylsulphinyl, n- or i-propylsulphinyl, methylsulphonyl,
ethylsulphonyl, n- or i-propylsulphonyl, represents methylamino,
ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino,
dimethylamino, diethylamino, di-n-propylamino or di-i-propylamino,
represents in each case optionally fluorine- and/or
chlorine-substituted ethenyl, propenyl, butenyl, ethinyl, propinyl,
butinyl, propenyloxy, butenyloxy, propenylthio, butenylthio,
propenylamino or butenylamino, represents in each case optionally
fluorine- and/or chlorine-substituted cyclopropyl, cyclobutyl,
cyclopentyl, cyclohexyl, cyclopropyloxy, cyclobutyloxy,
cyclopentyloxy, cyclohexyloxy, cyclopropylthio, cyclobutylthio,
cyclopentylthio, cyclohexylthio, cyclopropylamino, cyclobutylamino,
cyclopentylamino, cyclohexylamino, cyclopropylmethyl,
cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl,
cyclopropylmethoxy, cyclobutylmethoxy, cyclopentylmethoxy,
cyclohexylmethoxy, cyclopropylmethylthio, cyclobutylmethylthio,
cyclopentylmethylthio, cyclohexylmethylthio,
cyclopropylmethylamino, cyclobutylmethylamino,
cyclopentylmethylamino or cyclohexylmethylamino, or represents in
each case optionally fluorine-, chlorine-, methyl-, ethyl-, n- or
i-propyl-, n-, i-, s- or t-butyl-, methoxy-, ethoxy-, n- or
i-propoxy-substituted phenyl, phenyloxy, phenylthio, phenylamino,
benzyl, benzyloxy, benzylthio or benzylamino, represents
pyrrolidino, piperidino or morpholino, or--if two adjacent radicals
R.sup.14 and R.sup.14 are located at a double bond--together with
the adjacent radical R.sup.14 also represents a benzo grouping, and
R.sup.15 represents hydrogen, hydroxyl, amino, represents in each
case optionally fluorine- and/or chlorine-, methoxy- or
ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i- or
s-butyl, methoxy, ethoxy, n- or i-propoxy, methylamino, ethylamino
or dimethylamino, represents in each case optionally fluorine-
and/or chlorine-substituted ethenyl, propenyl, ethinyl, propinyl or
propenyloxy, represents in each case optionally fluorine- and/or
chlorine-substituted cyclopropyl, cyclobutyl, cyclopentyl,
cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl,
cyclohexylmethyl, or represents in each case optionally fluorine-,
chlorine-, methyl-, ethyl-, n- or i-propyl-, n-, i-, s- or
t-butyl-, methoxy-, ethoxy-, n- or i-propoxy-substituted phenyl or
benzyl, or together with an adjacent radical R.sup.14 or R.sup.15
represents in each case optionally methyl- and/or ethyl-substituted
propane-1,3-diyl(trimethylene) or
butane-1,4-diyl(tetramethylene).
15. A compound of the formula (I) according to claim 12 wherein m
represents the number 0, 1 or 2, A represents methylene or
dimethylene, R.sup.2 represents hydrogen, nitro, cyano, fluorine,
chlorine, bromine, iodine, methyl, ethyl, difluoromethyl,
trifluoromethyl, dichloromethyl, trichloromethyl, methoxymethyl,
methylthiomethyl, methylsulphinylmethyl, methylsulphonylmethyl,
methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, methylthio,
ethylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl,
ethylsulphonyl or dimethylaminosulphonyl, R.sup.3 represents nitro,
cyano, fluorine, chlorine, bromine, iodine, methyl, ethyl,
difluoromethyl, trifluoromethyl, dichloromethyl, trichloromethyl,
methoxymethyl, methylthiomethyl, methylsulphinylmethyl,
methylsulphonylmethyl, methoxy, ethoxy, difluoromethoxy,
trifluoromethoxy, methylthio, ethylthio, methylsulphinyl,
ethylsulphinyl, methylsulphonyl, ethylsulphonyl or
dimethylaminosulphonyl, R.sup.5 represents in each case optionally
fluorine- or chlorine-substituted methyl, ethyl, n- or i-propyl,
methylthio, ethylthio, n- or i-propylthio, represents phenyl, or
optionally also--if m represents 2--together with a second radical
R.sup.5 represents ethane-1,2-diyl(dimethylene),
propane-1,3-diyl(trimethylene) or butane-1,4-diyl(tetramethylene),
R.sup.6 represents hydroxyl, formyloxy, represents in each case
optionally fluorine-, chlorine-, methoxy- or ethoxy-substituted
methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or
i-propylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl,
ethylsulphonyl, acetyloxy, propionyloxy, n- or i-butyroyloxy,
methoxycarbonyloxy, ethoxycarbonyloxy, n- or i-propoxycarbonyloxy,
methylaminocarbonyloxy, ethylaminocarbonyloxy, n- or
i-propylaminocarbonyloxy, methylsulphonyloxy, ethylsulphonyloxy, n-
or i-propylsulphonyloxy, represents propenyloxy or propinyloxy, or
represents in each case optionally nitro-, cyano-, fluorine-,
chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-,
trifluoromethyl-, methoxy-, ethoxy-, n- or i-propoxy-,
difluoromethoxy- or trifluoromethoxy-substituted phenoxy,
phenylthio, phenylsulphinyl, phenylsulphonyl, benzoyloxy,
benzoylmethoxy, phenylsulphonyloxy, phenylmethoxy,
phenylmethylthio, phenylmethylsulphinyl or phenylmethylsulphonyl,
R.sup.10 represents hydrogen, cyano, fluorine, chlorine, bromine,
or represents in each case optionally fluorine-, chlorine-,
methoxy-, ethoxy-, n- or i-propoxy-substituted methyl, ethyl, n- or
i-propyl, acetyl, propionyl, n- or i-butyroyl, methoxy, ethoxy, n-
or i-propoxy, methoxycarbonyl, ethoxycarbonyl, n- or
i-propoxycarbonyl, methylthio, ethylthio, n- or i-propylthio,
methylsulphinyl, ethylsulphinyl, methylsulphonyl or ethylsulphonyl,
R.sup.11 represents hydrogen, represents in each case optionally
fluorine-, chlorine-, bromine-, methoxy- or ethoxy-substituted
methyl, ethyl, n- or i-propyl, or represents in each case
optionally fluorine-, chlorine-, bromine-, methyl- or
ethyl-substituted cyclopropyl, R.sup.12 represents hydrogen,
represents in each case optionally fluorine-, chlorine-, methoxy-
or ethoxy-substituted methyl, ethyl, n- or i-propyl, or represents
in each case optionally fluorine-, chlorine-, bromine-, methyl- or
ethyl-substituted cyclopropyl, R.sup.13 represents hydrogen, cyano,
fluorine, chlorine, bromine, or represents in each case optionally
fluorine-, chlorine-, bromine-, methoxy- or ethoxy-substituted
methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy,
methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl,
methylthio, ethylthio, n- or i-propylthio, methylsulphinyl,
ethylsulphinyl, n- or i-propylsulphinyl, methylsulphonyl,
ethylsulphonyl, n- or i-propylsulphonyl, R.sup.14 represents
hydrogen, hydroxyl, mercapto, cyano, fluorine, chlorine, bromine,
iodine, represents in each case optionally fluorine-, chlorine-,
methoxy-, ethoxy-, n- or i-propoxy-, methylthio-, ethylthio-, n- or
i-propylthio-, methylsulphinyl-, ethylsulphinyl-, n- or
i-propylsulphinyl-, methylsulphonyl-, ethylsulphonyl-, n- or
i-propylsulphonyl-substituted methyl, ethyl, n- or i-propyl,
methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or
i-propylthio, methylsulphinyl, ethylsulphinyl, n- or
i-propylsulphinyl, methylsulphonyl, ethylsulphonyl, n- or
i-propylsulphonyl, represents methylamino, ethylamino, n- or
i-propylamino, dimethylamino or diethylamino, represents in each
case optionally fluorine- and/or chlorine-substituted ethenyl,
propenyl, ethinyl, propinyl, propenyloxy, propenylthio or
propenylamino, represents in each case optionally fluorine- and/or
chlorine-substituted cyclopropyl, cyclopropyloxy, cyclopropylamino,
cyclopropylmethyl, cyclopropylmethoxy or cyclopropylmethylamino, or
represents in each case optionally fluorine-, chlorine-, methyl-,
ethyl-, n- or i-propyl-, methoxy-, ethoxy-, n- or
i-propoxy-substituted phenyl, phenyloxy, phenylthio, phenylamino,
benzyl, benzyloxy, benzylthio or benzylamino, or--if two adjacent
radicals R.sup.14 and R.sup.14 are located at a double
bond--together with the adjacent radical R.sup.14 also represents a
benzo grouping, and R.sup.15 represents hydrogen, hydroxyl, amino,
represents in each case optionally fluorine- and/or chlorine-,
methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl,
methoxy, ethoxy, n- or i-propoxy, methylamino, ethylamino or
dimethylamino, represents propenyl or propinyl, represents in each
case optionally fluorine- and/or chlorine-substituted cyclopropyl,
cyclobutyl or cyclopropylmethyl, or represents in each case
optionally fluorine-, chlorine-, methyl-, ethyl-, n- or i-propyl-,
methoxy-, ethoxy-, n- or i-propoxy-substituted phenyl or benzyl, or
together with an adjacent radical R.sup.14 or R.sup.15 represents
in each case optionally methyl- and/or ethyl-substituted
propane-1,3-diyl(trimethylene- ) or
butane-1,4-diyl(tetramethylene).
16. A process for preparing a compound of the formula (I) according
to claim 12 comprising the step of: (a) reacting a substituted
benzoic acid of the formula (II) 232wherein n, A, R.sup.2, R.sup.3
and R.sup.4 are each as defined in claim 12, or reactive
derivatives of said substituted benzoic acid, said reactive
deriviatives optionally being selected from the group consisting of
corresponding acid halides, acid cyanides and esters with a
compound of the formula (III) R.sup.1--H (III) wherein R.sup.1 is
as defined in claim 12, optionally in the presence of a dehydrating
agent, optionally in the presence of one or more reaction
auxiliaries and optionally in the presence of a diluent, or (b)
reacting a substituted benzoyl ketone of the formula (Ia)
233wherein n, A, R.sup.2, R.sup.3, R.sup.4 and R.sup.11 are each as
defined in claim 12, with an orthoformic ester or a
N,N-dimethyl-formamide acetal or with a cyanoformic ester or with
carbon disulphide and an alkylating agent, and then with
hydroxylamine or an acid adduct thereof, optionally in the presence
of one or more reaction auxiliaries and optionally in the presence
of one or more diluents, and, optionally, following the the step of
said process (a) or said process (b) according to the invention,
subjecting the resulting compound of the formula (I) to one or more
substitution, oxidation or reduction reactions within the scope of
the definition of the substituents and/or converting the compounds
of the formula (I) into salt-like compounds.
17. A compound of the formula (II) 234wherein n, A, R.sup.2,
R.sup.3 and R.sup.4 are each as defined in claim 12, and reactive
derivatives thereof.
18. A process for preparing a compound of the formula (II)
according to claim 17 comprising the step of: (.alpha.) reacting a
compound of the formula (IV) 235wherein n, A, R.sup.2 and R.sup.3
are each as defined in claim 12 and X.sup.1 represents halogen or
represents alkylsulphonyloxy or derivatives thereof with a
heterocyclic compound of the formula (V) H--R.sup.4 (V) wherein
R.sup.4 is as defined in claim 12, optionally in the presence of an
acid acceptor and optionally in the presence of a diluent, at
temperatures between 10.degree. C. and 150.degree. C., optionally
followed by one or more additional conversion reactions within the
scope of the definition of the substituents, or (.beta.) reacting a
compound of the formula (VI) 236wherein n, R.sup.2 and R.sup.3 are
each as defined in claim 12, or derivatives thereof with a
hydroxyalkylheterocycle of the formula (VII) 237wherein A and
R.sup.4 are each as defined in claim 12, in the presence of one or
more condensing agents and, optionally, in the presence of a
diluent, at temperatures between -20.degree. C. and +50.degree. C.,
optionally followed by one or more additional conversion reactions
within the scope of the definition of the substituents, or
(.gamma.) reacting a compound of the formula (VI) 238wherein n,
R.sup.2 and R.sup.3 are each as defined in claim 12, or derivatives
thereof with a halogenoalkylheterocycle of the formula (VIII)
239wherein A and R.sup.4 are each as defined in claim 12 and
X.sup.2 represents halogen, represents alkylsulphonyloxy or
represents arylsulphonyloxy, optionally in the presence of an acid
acceptor and optionally in the presence of a diluent, at
temperatures between 0.degree. C. and 150.degree. C., optionally
followed by one or more additional conversion reactions within the
scope of the definition of the substituents.
19. A compound of the formula (Ia) 240wherein n, A, R.sup.2,
R.sup.3, R.sup.4 and R.sup.11 are each as defined in claim 12.
20. A method for controlling one or more undesirable plants,
comprising the step of allowing at least one compound of the
formula (I) according to claim 12 to act on said one or more
undesirable plants and/or their habitats.
Description
[0001] The invention relates to novel substituted aryl ketones, to
processes for their preparation and to their use as herbicides.
[0002] It is already known that certain substituted aryl ketones
have herbicidal properties (cf. EP-A-090262, EP-A-135191,
EP-A-186118, EP-A-186119, EP-A-186120, EP-A-319075, EP-A-352543,
EP-A418175, EP-A-487357, EP-A-527036, EP-A-527037, EP-A-560483,
EP-A-609797, EP-A-609798, EP-A-625505, EP-A-625508, EP-A-636622,
U.S. Pat. No. 5,804,532, U.S. Pat. No. 5,834,402, U.S. Pat. No.
5,846,906, U.S. Pat. No. 5,863,865, WO-A-96/26192, WO-A-96/26193,
WO-A-96/26200, WO-A-96/26206, WO-A-97/27187, WO-A-97/35850,
WO-A-97/41105, WO-A,97/41116, WO-A-97/41117, WO-A-97/41118,
WO-A-97/43270, WO-A-97/46530, WO-A-98/28981, WO-A-98/31681,
WO-A-98/31682, WO-A-99/03856, WO-A-99/07688, WO-A-99/10327,
WO-A-99/10328). However, the activity of these compounds is not
entirely satisfactory.
[0003] This invention, accordingly, provides the novel substituted
aryl ketones of the general formula (I) 3
[0004] in which
[0005] n represents the number 0, 1 or 2,
[0006] A represents alkanediyl (alkylene),
[0007] R.sup.1 represents one of the groupings below 4
[0008] where
[0009] m represents the numbers 0 to 6,
[0010] R.sup.5 represents halogen or represents in each case
optionally substituted alkyl, alkylthio or aryl or--if m represents
2--optionally also together with a second radical R.sup.5
represents alkanediyl (alkylene),
[0011] R.sup.6 represents hydroxyl, formyloxy, halogen, or
represents in each case optionally substituted alkoxy, alkylthio,
alkylsulphinyl, alkylsulphonyl, alkylcarbonyloxy,
alkoxycarbonyloxy, alkylaminocarbonyloxy, alkylsulphonyloxy,
alkenyloxy, alkinyloxy, aryloxy, arylthio, arylsulphinyl,
arylsulphonyl, arylcarbonyloxy, arylcarbonylalkoxy,
arylsulphonyloxy, arylalkoxy, arylalkylthio, arylalkylsulphinyl or
arylalkylsulphonyl,
[0012] R.sup.7 represents hydrogen, cyano, carbamoyl,
thiocarbamoyl, halogen, or represents in each case optionally
substituted alkyl, alkoxy, alkylthio, alkylsulphinyl,
alkylsulphonyl, alkoxycarbonyl or cycloalkyl,
[0013] R.sup.8 represents hydrogen or represents in each case
optionally substituted alkyl, alkenyl, alkinyl, cycloalkyl,
cycloalkylalkyl, aryl or arylalkyl,
[0014] R.sup.9 represents hydroxyl, formyloxy, or represents in
each case optionally substituted alkoxy, alkylcarbonyloxy,
alkoxycarbonyloxy, alkylaminocarbonyloxy, alkylsulphonyloxy,
alkenyloxy, alkinyloxy, arylalkoxy, arylcarbonyloxy,
arylcarbonylalkoxy or arylsulphonyloxy,
[0015] R.sup.10 represents hydrogen, cyano, carbamoyl,
thiocarbamoyl, halogen, or represents in each case optionally
substituted alkyl, alkylcarbonyl, alkoxy, alkoxycarbonyl,
alkylthio, alkylsulphinyl or alkylsulphonyl,
[0016] R.sup.11 represents hydrogen or represents in each case
optionally substituted alkyl or cycloalkyl,
[0017] R.sup.12 represents hydrogen or represents in each case
optionally substituted alkyl or cycloalkyl, and
[0018] R.sup.13 represents hydrogen, cyano, carbamoyl, halogen, or
represents in each case optionally substituted alkyl, alkoxy,
alkoxycarbonyl, alkylthio, alkylsulphinyl or alkylsulphonyl,
[0019] R.sup.2 represents hydrogen, nitro, cyano, carboxyl,
carbamoyl, thiocarbamoyl, halogen, or represents in each case
optionally substituted alkyl, alkoxy, alkylthio, alkylsulphinyl,
alkylsulphonyl, alkylamino, dialkylamino or
dialkylaminosulphonyl,
[0020] R.sup.3 represents nitro, cyano, carboxyl, carbamoyl,
thiocarbamoyl, halogen, or represents in each case optionally
substituted alkyl, alkoxy, alkylthio, alkylsulphinyl,
alkylsulphonyl, alkylamino, dialkylamino or dialkylaminosulphonyl,
and
[0021] R.sup.4 represents an optionally substituted 4- to
12-membered, saturated or unsaturated, monocyclic or bicyclic
heterocyclic grouping which contains 1 to 4 hetero atoms (up to 4
nitrogen atoms and optionally--alternatively, or additionally--one
or two oxygen atoms or one or two sulphur atoms, or one or two SO
groupings or one or two SO.sub.2 groupings), and which additionally
contains one to three oxo groups (C.dbd.O) and/or thioxo groups
(C.dbd.S) as components of the heterocycle,
[0022] including all possible tautomeric forms of the compounds of
the general formula (I) and the possible salts and acid or base
adducts of the compounds of the general formula (I)-.
[0023] In the definitions, the hydrocarbon chains, such as alkyl or
alkanediyl, are in each case straight-chain or branched--including
in combination with heteroatoms, such as in alkoxy.
[0024] The compounds of the general formula (I) according to the
invention may contain one or more asymmetrically substituted carbon
atoms, and they may therefore be present in different enantiomeric
(R-- and S-configured forms) or diastereomeric forms. The invention
relates both to the various possible individual enantiomeric or
stereoisomeric forms of the compounds of the general formula (I)
and to the mixtures of these stereoisomeric compounds.
[0025] Preferred substituents or preferred ranges of the radicals
present in the formulae listed above and below are defined
below.
[0026] n preferably represents the number 0 or 1.
[0027] m preferably represents the number 0, 1, 2, 3 or 4.
[0028] A preferably represents alkanediyl (alkylene) having 1 to 6
carbon atoms.
[0029] R.sup.1 preferably represents one of the groupings below
5
[0030] R.sup.2 preferably represents hydrogen, nitro, cyano,
carboxyl, carbamoyl, thiocarbamoyl, halogen, or represents in each
case optionally cyano-, halogen-, C.sub.1-C.sub.4-alkoxy-,
C.sub.1-C.sub.4-alkylthio-, C.sub.1-C.sub.4-alkylsulphinyl- or
C.sub.1-C.sub.4-alkylsulphonyl-substit- uted alkyl, alkoxy,
alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino, dialkylamino
or dialkylaminosulphonyl having in each case 1 to 6 carbon atoms in
the alkyl groups.
[0031] R.sup.3 preferably represents nitro, cyano, carboxyl,
carbamoyl, thiocarbamoyl, halogen, or represents in each case
optionally cyano, halogen, C.sub.1-C.sub.4-alkoxy-,
C.sub.1-C.sub.4-alkylthio-, C.sub.1-C.sub.4-alkylsulphinyl- or
C.sub.1-C.sub.4-alkylsulphonyl-substit- uted alkyl, alkoxy,
alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino, dialkylamino
or dialkylaminosulphonyl having in each case 1 to 6 carbon atoms in
the alkyl groups.
[0032] R.sup.4 preferably represents one of the heterocyclic
groupings below 67
[0033] where in each case the broken bond is a single bond or a
double bond.
[0034] Q represents oxygen or sulphur,
[0035] R.sup.14 represents hydrogen, hydroxyl, mercapto, cyano,
halogen, represents in each case optionally cyano-, halogen-,
C.sub.1-C.sub.4-alkoxy-, C.sub.1-C.sub.4-alkylthio-,
C.sub.1-C.sub.4-alkylsulphinyl- or
C.sub.1-C.sub.4-alkylsulphonyl-substit- uted alkyl, alkylcarbonyl,
alkoxy, alkoxycarbonyl, alkylthio, alkylsulphinyl or alkylsulphonyl
having in each case up to 6 carbon atoms in the alkyl groups,
represents in each case optionally halogen-substituted alkylamino
or dialkylamino having in each case up to 6 carbon atoms in the
alkyl groups, represents in each case optionally
halogen-substituted alkenyl, alkinyl, alkenyloxy, alkenylthio or
alkenylamino having in each case up to 6 carbon atoms in the
alkenyl or alkinyl groups, represents in each case optionally
halogen-substituted cycloalkyl, cycloalkyloxy, cycloalkylthio,
cycloalkylamino, cycloalkylalkyl, cycloalkylalkoxy,
cycloalkylalkylthio or cycloalkylalkylamino having in each case 3
to 6 carbon atoms in the cycloalkyl groups and optionally up to 4
carbon atoms in the alkyl moiety, or represents in each case
optionally halogen-, C.sub.1-C.sub.4-alkyl- or
C.sub.1-C.sub.4-alkoxy-substituted phenyl, phenyloxy, phenylthio,
phenylamino, benzyl, benzyloxy, benzylthio or benzylamino,
represents pyrrolidino, piperidino or morpholino, or--if two
adjacent radicals R.sup.14 and R.sup.14 are located at a double
bond--also together with the adjacent radical R.sup.14 represents a
benzo grouping, and
[0036] R.sup.15 represents hydrogen, hydroxyl, amino,
alkylideneamino having up to 4 carbon atoms, represents in each
case optionally halogen- or C.sub.1-C.sub.4-alkoxy-substituted
alkyl, alkoxy, alkylamino, dialkylamino or alkanoylamino having in
each case up to 6 carbon atoms in the alkyl groups, represents in
each case optionally halogen-substituted alkenyl, alkinyl or
alkenyloxy having in each case up to 6 carbon atoms in the alkenyl
or alkinyl groups, represents in each case optionally
halogen-substituted cycloalkyl, cycloalkylalkyl or cycloalkylamino
having in each case 3 to 6 carbon atoms in the cycloalkyl groups
and optionally up to 3 carbon atoms in the alkyl moiety, or
represents in each case optionally halogen-, C.sub.1-C.sub.4-alkyl-
or C.sub.1-C.sub.4-alkoxy-sub- stituted phenyl or benzyl, or
together with an adjacent radical R.sup.14 or R.sup.15 represents
optionally halogen- or C.sub.1-C.sub.4-alkyl-subst- ituted
alkanediyl having 3 to 5 carbon atoms,
[0037] where the individual radicals R.sup.14 and R.sup.15--if more
than one of them are attached to the same heterocyclic
groupings--can have identical or different meanings within the
scope of the above definition.
[0038] R.sup.5 preferably represents halogen, represents in each
case optionally cyano-, halogen- or
C.sub.1-C.sub.4-alkoxy-substituted alkyl or alkylthio having in
each case 1 to 6 carbon atoms, represents optionally halogen-,
C.sub.1-C.sub.4-alkyl- or C.sub.1-C.sub.4-alkoxy-sub- stituted
phenyl, or optionally also--if m represents 2--together with a
second radical R.sup.5 represents alkanediyl (alkylene) having 2 to
6 carbon atoms.
[0039] R.sup.6 preferably represents hydroxyl, formyloxy, or
represents in each case optionally cyano-, halogen- or
C.sub.1-C.sub.4-alkoxy-substitut- ed alkoxy, alkylthio,
alkylsulphinyl, alkylsulphonyl, alkylcarbonyloxy,
alkoxycarbonyloxy, alkylaminocarbonyloxy or alkylsulphonyloxy
having in each case 1 to 6 carbon atoms in the alkyl groups,
represents in each case optionally cyano- or halogen-substituted
alkenyloxy or alkinyloxy having in each case 2 to 6 carbon atoms,
or represents in each case optionally nitro-, cyano-, halogen-,
C.sub.1-C.sub.4-alkyl-, C.sub.1-C.sub.4-halogenoalkyl-,
C.sub.1-C.sub.4-alkoxy- or
C.sub.1-C.sub.4-halogenoalkoxy-substituted aryloxy, arylthio,
arylsulphinyl, arylsulphonyl, arylcarbonyloxy, arylcarbonylalkoxy,
arylsulphonyloxy, arylalkoxy, arylalkylthio, arylalkylsulphinyl or
arylalkylsulphonyl having in each case 6 or 10 carbon atoms in the
aryl group and optionally 1 to 4 carbon atoms in the alkyl
moiety.
[0040] R.sup.7 preferably represents hydrogen, cyano, carbamoyl,
thiocarbamoyl, halogen, represents in each case optionally cyano-,
halogen- or C.sub.1-C.sub.4-alkoxy-substituted alkyl, alkoxy,
alkylthio, alkylsulphinyl, alkylsulphonyl or alkoxycarbonyl having
in each case 1 to 6 carbon atoms in the alkyl groups, or represents
optionally cyano-, halogen- or C.sub.1-C.sub.4-alkyl-substituted
cycloalkyl having 3 to 6 carbon atoms.
[0041] R.sub.8 preferably represents hydrogen, represents in each
case optionally cyano-, halogen- or
C.sub.1-C.sub.4-alkoxy-substituted alkyl having 1 to 6 carbon
atoms, represents in each case optionally cyano- or
halogen-substituted alkenyl or alkinyl having in each case 2 to 6
carbon atoms, represents in each case optionally cyano-, halogen-
or C.sub.1-C.sub.4-alkyl-substituted cycloalkyl or cycloalkylalkyl
having in each case 3 to 6 carbon atoms in the cycloalkyl group and
optionally 1 to 4 carbon atoms in the alkyl moiety, or represents
in each case optionally nitro-, cyano-, halogen-,
C.sub.1-C.sub.4-alkyl-, C.sub.1-C.sub.4-halogen- oalkyl-,
C.sub.1-C.sub.4-alkoxy- or C.sub.1-C.sub.4-halogenoalkoxy-substit-
uted aryl or arylalkyl having in each case 6 or 10 carbon atoms in
the aryl group and optionally 1 to 4 carbon atoms in the alkyl
moiety.
[0042] R.sup.9 preferably represents hydroxyl, formyloxy,
represents in each case optionally cyano-, halogen- or
C.sub.1-C.sub.4-alkoxy-substitut- ed alkoxy, alkylcarbonyloxy,
alkoxycarbonyloxy, alkylaminocarbonyloxy or alkylsulphonyloxy
having in each case 1 to 6 carbon atoms in the alkyl groups,
represents in each case optionally cyano- or halogen-substituted
alkenyloxy or alkinyloxy having in each case 2 to 6 carbon atoms,
or represents in each case optionally nitro-, cyano-, halogen-,
C.sub.1-C.sub.4-alkyl-, C.sub.1-C.sub.4-halogenoalkyl-,
C.sub.1-C.sub.4-alkoxy- or
C.sub.1-C.sub.4-halogenoalkoxy-substituted arylalkoxy,
arylcarbonyloxy, arylcarbonylalkoxy or arylsulphonyloxy having in
each case 6 or 10 carbon atoms in the aryl group and optionally 1
to 4 carbon atoms in the alkyl moiety.
[0043] R.sup.10 preferably represents hydrogen, cyano, carbamoyl,
thiocarbamoyl, halogen, or represents in each case optionally
cyano-, halogen- or C.sub.1-C.sub.4-alkoxy-substituted alkyl,
alkylcarbonyl, alkoxy, alkoxycarbonyl, alkylthio, alkylsulphinyl or
alkylsulphonyl having in each case 1 to 6 carbon atoms in the alkyl
groups.
[0044] R.sup.11 preferably represents hydrogen, represents
optionally cyano-, halogen- or C.sub.1-C.sub.4-alkoxy-substituted
alkyl having 1 to 6 carbon atoms or represents optionally cyano-,
halogen- or C.sub.1-C.sub.4-alkyl-substituted cycloalkyl having 3
to 6 carbon atoms.
[0045] R.sup.12 preferably represents hydrogen, represents
optionally cyano-, halogen- or C.sub.1-C.sub.4-alkoxy-substituted
alkyl having 1 to 6 carbon atoms or represents optionally cyano-,
halogen- or C.sub.1-C.sub.4-alkyl-substituted cycloalkyl having 3
to 6 carbon atoms.
[0046] R.sup.13 preferably represents hydrogen; cyano, carbamoyl,
halogen, or represents in each case optionally cyano-, halogen- or
C.sub.1-C.sub.4-alkoxy-substituted alkyl, alkoxy, alkoxycarbonyl,
alkylthio, alkylsulphinyl or alkylsulphonyl having in each case 1
to 6 carbon atoms in the alkyl groups.
[0047] m particularly preferably represents the numbers 0, 1, 2 or
3.
[0048] A particularly preferably represents methylene,
ethane-1,2-diyl(dimethylene), ethane-1,1-diyl, propane-1,2-diyl,
propane-1,3-diyl(trimethylene), butane-1,2-diyl, butane-1,3-diyl or
butane-1,4-diyl(tetramethylene).
[0049] R.sup.2 particularly preferably represents hydrogen, nitro,
cyano, carboxyl, carbamoyl, thiocarbamoyl, fluorine, chlorine,
bromine, iodine, or represents in each case optionally fluorine-
and/or chlorine-, methoxy-, ethoxy-, n- or i-propoxy-, methylthio-,
ethylthio-, n- or i-propylthio-, methylsulphinyl-, ethylsulphinyl-,
methylsulphonyl- or ethylsulphonyl-substituted methyl, ethyl, n- or
i-propyl, n-, i-, s- or t-butyl, represents in each case optionally
fluorine- and/or chlorine-, methoxy-, ethoxy-, n- or
i-propoxy-substituted methoxy, ethoxy, n- or i-propoxy, represents
in each case optionally fluorine- and/or chlorine-substituted
methylthio, ethylthio, n- or i-propylthio, methylsulphinyl,
ethylsulphinyl, n- or i-propylsulphinyl, methylsulphonyl,
ethylsulphonyl, n- or i-propylsulphonyl, or represents methylamino,
ethylamino, n- or i-propylamino, dimethylamino, diethylamino,
dimethylaminosulphonyl or diethylaminosulphonyl.
[0050] R.sup.3 particularly preferably represents nitro, cyano,
carboxyl, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine,
represents in each case optionally fluorine- and/or chlorine-,
methoxy-, ethoxy-, n- or i-propoxy-, methylthio-, ethylthio-, n- or
i-propylthio-, methylsulphinyl-, ethylsulphinyl-, methylsulphonyl-
or ethylsulphonyl-substituted methyl, ethyl, n- or i-propyl, n-,
i-, s- or t-butyl, represents in each case optionally fluorine-
and/or chlorine-, methoxy-, ethoxy-, n- or i-propoxy-substituted
methoxy, ethoxy, n- or i-propoxy, represents in each case fluorine-
and/or chorine-substituted methylthio, ethylthio, n- or
i-propylthio, methylsulphinyl, ethylsulphinyl, n- or
i-propylsulphinyl, methylsulphonyl, ethylsulphonyl, n- or
i-propylsulphonyl, or represents methylamino, ethylamino, n- or
i-propylamino, dimethylamino, diethylamino, dimethylaminosulphonyl
or diethylaminosulphonyl
[0051] R.sup.4 particularly preferably represents one of the
heterocyclic groupings below. 8
[0052] R.sup.5 particularly preferably represents fluorine,
chlorine, bromine, represents in each case optionally cyano-,
fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl,
n- or i-propyl, n-, i-, s- or t-butyl, methylthio, ethylthio, n- or
i-propylthio, n-, i-, s- or t-butylthio, represents optionally
fluorine-, chlorine-, methyl- or methoxy-substituted phenyl, or
optionally also--if m represents 2--together with a second radical
R.sup.5 represents ethane-1,2-diyl(dimethylene),
propane-1,3-diyl(trimethylene) or
butane-1,4-diyl(tetramethylene).
[0053] R.sup.6 particularly preferably represents hydroxyl,
formyloxy, represents in each case optionally cyano-, fluorine-,
chlorine-, methoxy- or ethoxy-substituted methoxy, ethoxy, n or
i-propoxy, n-, i-, s- or t-butoxy, methylthio, ethylthio, n- or
i-propylthio, n-, i-, s- or t-butylthio, methylsulphinyl,
ethylsulphinyl, n- or i-propylsulphinyl, methylsulphonyl,
ethylsulphonyl, n- or i-propylsulphonyl, acetyloxy, propionyloxy,
n- or i-butyroyloxy, methoxycarbonyloxy, ethoxycarbonyloxy, n- or
i-propoxycarbonyloxy, methylaminocarbonyloxy,
ethylaminocarbonyloxy, n- or i-propylaminocarbonyloxy,
methylsulphonyloxy, ethylsulphonyloxy, n- or i-propylsulphonyloxy,
represents in each case optionally cyano-, fluorine-, chlorine- or
bromine-substituted propenyloxy, butenyloxy, propinyloxy or
butinyloxy, or represents in each case optionally nitro-, cyano-,
fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-,
n-, i-, s- or t-butyl-, trifluoromethyl-; methoxy-, ethoxy-, n- or
i-propoxy-, n-, i-, s- or t-butoxy-, difluoromethoxy- or
trifluoromethoxy-substituted phenoxy, phenylthio, phenylsulphinyl,
phenylsulphonyl, benzoyloxy, benzoylmethoxy, phenylsulphonyloxy,
phenylmethoxy, phenylmethylthio, phenylmethylsulfonyl or
phenylmethylsulfonyl.
[0054] R.sup.7 particularly preferably represents hydrogen, cyano,
carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine, represents
in each case optionally cyano-, fluorine-, chlorine-, methoxy- or
ethoxy-substituted methyl, ethyl, n- or i-propyl, n-,.i-, s- or
t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy,
methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or
t-butylthio, methylsulphinyl, ethylsulphinyl, n- or
i-propylsulphinyl, methylsulphonyl, ethylsulphonyl, n- or
i-propylsulphonyl, methoxycarbonyl, ethoxycarbonyl, n- or
i-propoxycarbonyl, or represents in each case optionally cyano-,
fluorine-, chlorine-, bromine-, methyl- or ethyl-substituted
cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
[0055] R.sup.8 particularly preferably represents hydrogen,
represents in each case optionally cyano-, fluorine-, chlorine-,
bromine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or
i-propyl, n-, i-, s- or t-butyl, represents in each case optionally
cyano-, fluorine-, chlorine- or bromine-substituted propenyl,
butenyl, propinyl or butinyl, represents in each case optionally
cyano-, fluorine-, chlorine-, bromine-, methyl- or
ethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,
cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or
cyclohexylmethyl, or represents in each case optionally nitro-,
cyano-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or
i-propyl, n-, i-, s- or t-butyl, trifluoromethyl, methoxy, ethoxy,
n- or i-propoxy, n-, i-, s- or t-butoxy-, difluoromethoxy- or
trifluoromethoxy-substituted phenyl or benzyl.
[0056] R.sup.9 particularly preferably represents hydroxyl,
formyloxy, represents in each case optionally cyano-, fluorine-,
chlorine-, bromine-, methoxy-, ethoxy-, n- or i-propoxy-substituted
methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy,
acetyloxy, propionyloxy, n- or i-butyroyloxy, methoxycarbonyloxy,
ethoxycarbonyloxy, n- or i-propoxycarbonyloxy,
methylaminocarbonyloxy, ethylaminocarbonyloxy, n- or
i-propyl-aminocarbonyloxy, methylsulphonyloxy, ethylsulphonyloxy,
n- or i-propylsulphonyloxy, represents in each case optionally
cyano-, fluorine-, chlorine- or bromine-substituted propenyloxy,
butenyloxy, propinyloxy or butinyloxy, or represents in each case
optionally nitro-, cyano-, fluorine-, chlorine-, bromine-, methyl-,
ethyl-, n- or i-propyl-, n-, i-, s- or t-butyl-, trifluoromethyl-,
methoxy-, ethoxy-, n- or i-propoxy-, n-, i-, s- or t-butoxy-,
difluoromethoxy- or trifluoromethoxy-substituted phenylmethoxy,
benzoyloxy, benzoylmethoxy or phenyl-sulphonyloxy.
[0057] R.sup.10 particularly preferably represents hydrogen, cyano,
carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine, or
represents in each case optionally cyano-, fluorine-, chlorine-,
bromine-, methoxy-, ethoxy-, n- or i-propoxy-substituted methyl,
ethyl, n- or i-propyl, n-, i-, s- or t-butyl, acetyl, propionyl, n-
or i-butyroyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or
t-butoxy, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl,
methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or
t-butylthio, methylsulphinyl, ethylsulphinyl, n- or
i-propylsulphinyl, methylsulphonyl, ethylsulphonyl, n- or
i-propylsulphonyl.
[0058] R.sup.11 particularly preferably represents hydrogen,
represents in each case optionally cyano-, fluorine-, chlorine-,
bromine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or
i-propyl, n-, i-, s- or t-butyl, or represents in each case
optionally cyano-, fluorine-, chlorine-, bromine-, methyl- or
ethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl or
cyclohexyl.
[0059] R.sup.12 particularly preferably represents hydrogen,
represents in each case optionally cyano-, fluorine-, chlorine-,
bromine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or
i-propyl, n-, i-, s- or t-butyl, or represents in each case
optionally cyano-, fluorine-, chlorine-, bromine-, methyl- or
ethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl or
cyclohexyl.
[0060] R.sup.13 particularly preferably represents hydrogen, cyano,
carbamoyl, fluorine, chlorine, brornine, or represents in each case
optionally cyano-, fluorine-, chlorine-, bromine-, methoxy- or
ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or
t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy,
methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl,
methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or
t-butylthio, methylsulphinyl, ethylsulphinyl, n- or
i-propylsulphinyl, methylsulphonyl, ethylsulphonyl, n- or
i-propylsulphonyl.
[0061] R.sup.14 particularly preferably represents hydrogen,
hydroxyl, mercapto, cyano, fluorine, chlorine, bromine, iodine,
represents in each case optionally fluorine-, chlorine-, methoxy-,
ethoxy-, n- or i-propoxy-, n-, i-, s- or t-butoxy-, methylthio-,
ethylthio-, n- or i-propylthio-, n-, i-, s- or t-butylthio-,
methylsulphinyl-, ethylsulphinyl-, n- or i-propylsulphinyl-,
methylsulphonyl-, ethylsulphonyl-, n- or
i-propylsulphonyl-substituted methyl, ethyl, n- or i-propyl, n-,
i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or
t-butoxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or
t-butylthio, methylsulphinyl, ethylsulphinyl, n- or
i-propylsulphinyl, methylsulphonyl, ethylsulphonyl, n- or
i-propylsulphonyl, represents methylamino, ethylamino, n- or
i-propylamino, n-, i-, s-or t-butylamino, dimethylamino,
diethylamino, di-n-propylamino or di-i-propylamino, represents in
each case optionally fluorine- and/or chlorine-substituted ethenyl,
propenyl, butenyl, ethinyl, propinyl, butinyl, propenyloxy,
butenyloxy, propenylthio, butenylthio, propenylamino or
butenylamino, represents in each case optionally fluorine- and/or
chlorine-substituted cyclopropyl, cyclobutyl, cyclopentyl,
cyclohexyl, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy,
cyclohexyloxy, cyclopropylthio, cyclobutylthio, cyclopentylthio,
cyclohexylthio, cyclopropylamino, cyclobutylamino,
cyclopentylamino, cyclohexylamino, cyclopropylmethyl,
cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl,
cyclopropylmethoxy, cyclobutylmethoxy, cyclopentylmethoxy,
cyclohexylmethoxy, cyclopropylmethylthio, cyclobutylmethylthio,
cyclopentylmethylthio, cyclohexylmethylthio,
cyclopropylmethylamino, cyclobutylmethylamino,
cyclopentylmethylamino or cyclohexylmethylamino, or represents in
each case optionally fluorine-, chlorine-, methyl-, ethyl-, n- or
i-propyl-, n-, i-, s- or t-butyl-, methoxy-, ethoxy-, n- or
i-propoxy-substituted phenyl, phenyloxy, phenylthio, phenylamino,
benzyl, benzyloxy, benzylthio or benzylamino, represents
pyrrolidino, piperidino or morpholino, or--if two adjacent radicals
R.sup.14 and R.sup.14 are located at a double bond--together with
the adjacent radical R.sup.14 also represents a benzo grouping.
[0062] R.sup.15 particularly preferably represents hydrogen,
hydroxyl, amino, represents in each case optionally fluorine-
and/or chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n-
or i-propyl, n-, i- or s-butyl, methoxy, ethoxy, n- or i-propoxy,
methylamino, ethylamino or dimethylamino, represents in each case
optionally fluorine- and/or chlorine-substituted ethenyl, propenyl,
ethinyl, propinyl or propenyloxy, represents in each case
optionally fluorine- and/or chlorine-substituted cyclopropyl,
cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl,
cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, or
represents in each case optionally fluorine-, chlorine-, methyl-,
ethyl-, n- or i-propyl-, n-, i-, s- or t-butyl-, methoxy-, ethoxy-,
n- or i-propoxy-substituted phenyl or benzyl, or together with an
adjacent radical R.sup.14 or R.sup.15 represents in each case
optionally methyl- and/or ethyl-substituted
propane-1,3-diyl(trimethylene) or
butane-1,4-diyl(tetramethylene).
[0063] A very particularly preferably represents methylene or
dimethylene.
[0064] m very particularly preferably represents the number 0, 1 or
2,
[0065] R.sup.2 very particularly preferably represents hydrogen,
nitro, cyano, fluorine, chlorine, bromine, iodine, methyl, ethyl,
difluoromethyl, trifluoromethyl, dichloromethyl, trichloromethyl,
methoxymethyl, methylthiomethyl, methylsulphinylmethyl,
methylsulphonylmethyl, methoxy, ethoxy, difluoromethoxy,
trifluoromethoxy, methylthio, ethylthio, methylsulphinyl,
ethylsulphinyl, methylsulphonyl, ethylsulphonyl or
dimethylaminosulphonyl.
[0066] R.sup.3 very particularly preferably represents nitro,
cyano, fluorine, chlorine, bromine, iodine, methyl, ethyl,
difluoromethyl, trifluoromethyl, dichloromethyl, trichloromethyl,
methoxymethyl, methylthiomethyl, methylsulphinylmethyl,
methylsulphonylmethyl, methoxy, ethoxy, difluoromethoxy,
trifluoromethoxy, methylthio, ethylthio, methylsulphinyl,
ethylsulphinyl, methylsulphonyl, ethylsulphonyl or
dimethylaminosulphonyl.
[0067] R.sup.5 very particularly preferably represents in each case
optionally fluorine- or chlorine-substituted methyl, ethyl, n- or
i-propyl, methylthio, ethylthio, n- or i-propylthio, represents
phenyl, or optionally also--if m represents 2--together with a
second radical R.sup.5 represents ethane-1,2-diyl(dimethylene),
propane-1,3-diyl(trimeth- ylene) or
butane-1,4-diyl(tetramethylene).
[0068] R.sup.6 very particularly preferably represents hydroxyl,
formyloxy, represents in each case optionally fluorine-, chlorine-,
methoxy- or ethoxy-substituted methoxy, ethoxy, n- or i-propoxy,
methylthio, ethylthio, n- or i-propylthio, methylsulphinyl,
ethylsulphinyl, methylsulphonyl, ethylsulphonyl, acetyloxy,
propionyloxy, n- or i-butyroyloxy, methoxycarbonyloxy,
ethoxycarbonyloxy, n- or i-propoxycarbonyloxy,
methylaminocarbonyloxy, ethylaminocarbonyloxy, n- or
i-propylaminocarbonyloxy, methylsulphonyloxy, ethylsulphonyloxy, n-
or i-propylsulphonyloxy, represents propenyloxy or propinyloxy, or
represents in each case optionally nitro-, cyano-, fluorine-,
chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-,
trifluoromethyl-, methoxy-, ethoxy-, n- or i-propoxy-,
difluoromethoxy- or trifluoromethoxy-substitut- ed phenoxy,
phenylthio, phenylsulphinyl, phenylsulphonyl, benzoyloxy,
benzoylmethoxy, phenylsulphonyloxy, phenylmethoxy,
phenylmethylthio, phenylmethylsulphinyl or
phenylmethylsulphonyl.
[0069] R.sup.7 very particularly preferably represents hydrogen,
cyano, fluorine, chlorine, bromine, represents in each case
optionally fluorine-, chlorine-, methoxy- or ethoxy-substituted
methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy,
methylthio, ethylthio, n- or i-propylthio, methylsulphinyl,
ethylsulphinyl, n- or i-propylsulphinyl, methylsulphonyl,
ethylsulphonyl, n- or i-propylsulphonyl, methoxycarbonyl,
ethoxycarbonyl, n- or i-propoxycarbonyl.
[0070] R.sup.8 very particularly preferably represents hydrogen,
represents in each case optionally cyano-, fluorine-, chlorine-,
methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl,
represents in each case optionally fluorine- or
chlorine-substituted propenyl or propinyl, represents optionally
fluorine-, chlorine-, bromine-, methyl- or ethyl-substituted
cyclopropyl, or represents in each case optionally fluorine-,
chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-,
trifluoromethyl-, methoxy-, ethoxy-, k n- or i-propoxy-,
difluoromethoxy- or trifluoromethoxy-substituted phenyl or
benzyl.
[0071] R.sup.9 very particularly preferably represents hydroxyl,
formyloxy, represents in each case optionally cyano-, fluorine-,
chlorine-, bromine-, methoxy-, ethoxy-, n- or i-propoxy-substituted
methoxy, ethoxy, n- or i-propoxy, acetyloxy, propionyloxy, n- or
i-butyroyloxy, methoxycarbonyloxy, ethoxycarbonyloxy, n- or
i-propoxycarbonyloxy, methylaminocarbonyloxy,
ethylaminocarbonyloxy, n- or i-propylaminocarbonyloxy,
methylsulphonyloxy, ethylsulphonyloxy, n- or i-propylsulphonyloxy,
represents propenyloxy or propinyloxy, or represents in each case
optionally nitro-, cyano-, fluorine-, chlorine-, bromine-, methyl-,
ethyl-, n- or i-propyl-, trifluoromethyl-, methoxy-, ethoxy-, n- or
i-propoxy-, difluoromethoxy- or trifluoromethoxy-substitut- ed
phenylmethoxy, benzoyloxy, benzoylmethoxy or
phenylsulphonyloxy.
[0072] R.sup.10 very particularly preferably represents hydrogen,
cyano, fluorine, chlorine, bromine, or represents in each case
optionally fluorine-, chlorine-, methoxy-, ethoxy-, n- or
i-propoxy-substituted methyl, ethyl, n- or i-propyl, acetyl,
propionyl, n- or i-butyroyl, methoxy, ethoxy, n- or i-propoxy,
methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl,
methylthio, ethylthio, n- or i-propylthio, methylsulphinyl,
ethylsulphinyl, methylsulphonyl or ethylsulphonyl.
[0073] R.sup.11 very particularly preferably represents hydrogen,
represents in each case optionally fluorine-, chlorine-, bromine-,
methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, or
represents in each case optionally fluorine-, chlorine-, bromine-,
methyl- or ethyl-substituted cyclopropyl.
[0074] R.sup.12 very particularly preferably represents hydrogen,
represents in each case optionally fluorine-, chlorine-, methoxy-
or ethoxy-substituted methyl, ethyl, n- or i-propyl, or represents
in each case optionally fluorine-, chlorine-, bromine-, methyl- or
ethyl-substituted cyclopropyl.
[0075] R.sup.13 very particularly preferably represents hydrogen,
cyano, fluorine, chlorine, bromine, or represents in each case
optionally fluorine-, chlorine-, bromine-, methoxy- or
ethoxy-substituted methyl, ethyl, n- or i-propyl, methoxy, ethoxy,
n- or i-propoxy, methoxycarbonyl, ethoxycarbonyl, n- or
i-propoxycarbonyl, methylthio, ethylthio, n- or i-propylthio,
methylsulphinyl, ethylsulphinyl, n- or i-propylsulphinyl,
methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl.
[0076] R.sup.14 very particularly preferably represents hydrogen,
hydroxyl, mercapto, cyano, fluorine, chlorine, bromine, iodine,
represents in each case optionally fluorine-, chlorine-, methoxy-,
ethoxy-, n- or i-propoxy-, methylthio-, ethylthio-, n- or
i-propylthio-, methylsulphinyl-, ethylsulphinyl-, n- or
i-propylsulphinyl-, methylsulphonyl-, ethylsulphonyl-, n- or
i-propylsulphonyl-substituted methyl, ethyl, n- or i-propyl,
methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or
i-propylthio, methylsulphinyl, ethylsulphinyl, n- or
i-propylsulphinyl, methylsulphonyl, ethylsulphonyl, n- or
i-propylsulphonyl, represents methylamino, ethylamino, n- or
i-propylamino, dimethylamino or diethylamino, represents in each
case optionally fluorine- and/or chlorine-substituted ethenyl,
propenyl, ethinyl, propinyl, propenyloxy, propenylthio or
propenylamino, represents in each case optionally fluorine- and/or
chlorine-substituted cyclopropyl, cyclopropyloxy, cyclopropylamino,
cyclopropylmethyl, cyclopropylmethoxy or cyclopropylmethylamino, or
represents in each case optionally fluorine-, chlorine-, methyl-,
ethyl-, n- or i-propyl-, methoxy-, ethoxy-, n- or
i-propoxy-substituted phenyl, phenyloxy, phenylthio, phenylamino,
benzyl, benzyloxy, benzylthio or benzylamino, or--if two adjacent
radicals R.sup.14 and R.sup.14 are located at a double
bond--together with the adjacent radical R.sup.14 also represents a
benzo grouping.
[0077] R.sup.15 very particularly preferably represents hydrogen,
hydroxyl, amino, represents in each case optionally fluorine-
and/or chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n-
or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylamino,
ethylamino or dimethylamino, represents propenyl or propinyl,
represents in each case optionally fluorine- and/or
chlorine-substituted cyclopropyl, cyclobutyl or cyclopropylmethyl,
or represents in each case optionally fluorine-, chlorine-,
methyl-, ethyl-, n- or i-propyl-, methoxy-, ethoxy-, n- or
i-propoxy-substituted phenyl or benzyl, or together with an
adjacent radical R.sup.14 or R.sup.15 represents in each case
optionally methyl- and/or ethyl-substituted
propane-1,3-diyl(trimethylene) or
butane-1,4-diyl(tetramethylene).
[0078] 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.
[0079] 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.
[0080] Very particular preference according to the invention is
given to the compounds of the formula (I) which contain a
combination of the meanings listed above as being very particularly
preferred.
[0081] Particular emphasis is given to the compounds of the general
formulae (I-1) to (I-3): 9
[0082] Here, n, A, R.sup.1, R.sup.2, R.sup.3 and R.sup.4 in each
case have the most preferred meaning.
[0083] Very particular emphasis is given to the compounds of the
general formulae (I-2A) to (I-2D): 10
[0084] Here, m, n, A, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6,
R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11, R.sup.12 and
R.sup.13 in each case have the most preferred meaning.
[0085] The invention also provides the sodium, potassium,
magnesium, calcium, ammonium, C.sub.1-C.sub.4-alkyl-ammonium,
di-(C.sub.1-C.sub.4-alkyl)-ammonium,
tri-(C.sub.1-C.sub.4-alkyl)-ammonium- ,
tetra-(C.sub.1-C.sub.4-alkyl)-ammonium,
tri-(C.sub.1-C.sub.4-alkyl)-sulp- honium, C.sub.5- or
C.sub.6-cycloalkyl-ammonium and
di-(C.sub.1-C.sub.2-alkyl)-benzyl-ammonium salts of compounds of
the formula (I) in which preferably n, A, R.sup.1, R.sup.2, R.sup.3
and R.sup.4 have the meanings given above as being preferred,
particularly preferred or very particularly preferred.
[0086] The general or preferred radical definitions given above
apply both to the end products of the formula (I) and,
correspondingly, to the starting materials or intermediates
required in each case for the preparation. These radical
definitions can be combined with one another as desired, i.e.
including combinations between the given preferred ranges.
[0087] The novel substituted aryl ketones of the general formula
(I) have strong and selective herbicidal activity.
[0088] the novel substituted aryl ketones of the general formula
(I) are obtained when
[0089] (a) substituted benzoic acids of the general formula (II).
11
[0090] in which
[0091] n, A, R.sup.2, R.sup.3 and R.sup.4 are each as defined
above,
[0092] or reactive derivatives thereof, such as, for example, the
corresponding acid halides, acid cyanides or esters
[0093] are reacted with compounds of the general formula (III)
R.sup.1--H (III)
[0094] in which
[0095] R.sup.1 is as defined above,
[0096] if appropriate in the presence of a dehydrating agent, if
appropriate in the presence of one or more reaction auxiliaries and
if appropriate in the presence of a diluent,
[0097] or where
[0098] (b) substituted benzoyl ketones of the general formula (Ia)
12
[0099] in which
[0100] n, A, R.sup.2, R.sup.3, R.sup.4 and R.sup.11 are each as
defined above,
[0101] are reacted with an orthoformic ester or a
N,N-dimethyl-formamide acetal or with a cyanoformic ester or with
carbon disulphide and an alkylating agent, and then with
hydroxylamine or an acid adduct thereof,
[0102] if appropriate in the presence of one or more reaction
auxiliaries and if appropriate in the presence of one or more
diluents,
[0103] and, if appropriate, following the practice of the process
(a) or (b) according to the invention, the resulting compounds of
the general formula (I) are subjected in a customary manner to
substitution, oxidation or reduction reactions within the scope of
the definition of the substituents and/or the compounds of the
general formula (I) are converted in a customary manner into
salt-like compounds.
[0104] Using; for example,
4-chloro-3-[(3,4-dimethyl-5-oxo-4,5-dihydro-1H--
1,2,4-triazol-3-yl)-methoxy]-2-fluoro-benzoic acid and
1,3-dimethyl-5-hydroxy-pyrazole as starting materials, the course
of the reaction in the process (a) according to the invention can
be illustrated by the following equation: 13
[0105] Using, for example,
1-[2-chloro-4-methyl-3-[2-(2-oxo-1(2H)-pyridiny-
l)-ethoxy]-phenyl]-3-cyclopropyl-1,3-propanedione, ethyl
cyanoformate and hydroxylamine as starting materials, the course of
the reaction in the process (b) according to the invention can be
illustrated by the following equation: 14
[0106] The formula (II) provides a general definition of the
substituted benzoic acids to be used as starting materials in the
process (a) according to the invention for preparing compounds of
the general formula (I). In the general formula (II), n, A,
R.sup.2, R.sup.3 and R.sup.4 each preferably have those meanings
which have already been mentioned above, in connection with the
description of the compounds of the general formula (I) according
to the invention, as being preferred, particularly preferred or
very particularly preferred for n, A, R.sup.2, R.sup.3 and
R.sup.4.
[0107] The starting materials of the general formula (II) have
hitherto not been disclosed in the literature; as novel substances,
they also form part of the subject-matter of the present
application.
[0108] The novel substituted benzoic acids--or else their
derivatives, such as their esters, in particular the methyl esters
and ethyl esters--are obtained when
[0109] (.alpha.) Compounds of the formula (IV) 15
[0110] in which
[0111] n, A, R.sup.2 and R.sup.3 are each as defined above and
[0112] X.sup.1 represents halogen (in particular fluorine, chlorine
or bromine) or represents alkylsulphonyloxy (in particular
methylsulphonyloxy or ethylsulphonyloxy),
[0113] or else their derivatives, such as their esters, in
particular the methyl esters and ethyl esters
[0114] are reacted with heterocyclic compounds of the general
formula (V)
H--R.sup.4 (V)
[0115] in which
[0116] R.sup.4 is as defined above,
[0117] if appropriate in the presence of an acid acceptor, such as,
for example, potassium carbonate, and if appropriate in the
presence of a diluent, such as, for example, acetone, butanone,
acetonitrile, N,N-dimethyl-formamide or dimethyl sulphoxide, at
temperatures between 10.degree. C. and 150.degree. C., followed, if
appropriate, by further customary conversion reactions within the
scope of the definition of the substituents (cf. the Preparation
Examples),
[0118] or when
[0119] (.beta.) Compounds of the formula (VI) 16
[0120] in which
[0121] n, R.sup.2 and R.sup.3 are each as defined above
[0122] or else their derivatives, such as their esters, in
particular the methyl esters and ethyl esters
[0123] are reacted with hydroxyalkylheterocycles of the general
formula (VII) 17
[0124] in which
[0125] A and R.sup.4 are each as defined above,
[0126] in the presence of condensing auxiliaries, such as, for
example, diethyl azodicarboxylate and triphenylphosphine, if
appropriate in the presence of a diluent, such as, for example,
tetrahydrofuran at temperatures between -20.degree. C. and
+50.degree. C., followed, if appropriate, by further customary
conversion reactions within the scope of the definition of the
substituents (cf. the Preparation Examples),
[0127] or when
[0128] (.gamma.) Compounds of the formula (VI) 18
[0129] in which
[0130] n, R.sup.2 and R.sup.3 are each as defined above,
[0131] or else their derivatives, such as their esters, in
particular the methyl esters and ethyl esters
[0132] are reacted with halogenoalkylheterocycles of the general
formula (VIII) 19
[0133] in which
[0134] A and R.sup.4 are each as defined above and
[0135] X.sup.2 represents halogen (in particular fluorine, chlorine
or bromine), represents alkylsulphonyloxy (in particular
methylsulphonyloxy or ethylsulphonyloxy), or represents
arylsulphonyloxy (in particular p-tolylsulphonyloxy),
[0136] if appropriate in the presence of an acid acceptor, such as,
for example, potassium carbonate or triethylamine, and if
appropriate in the presence of a diluent, such as, for example,
acetone, butanone, acetonitrile, N,N-dimethylformamide or dimethyl
sulphoxide, at temperatures between 0.degree. C. and 150.degree.
C., followed, if appropriate, by further customary conversion
reactions within the scope of the definition of the substituents
(cf. the Preparation Examples).
[0137] The formula (III) provides a general definition of the
compounds further to be used as starting materials in the process
(a) according to the invention for preparing compounds of the
general formula (I). In the general formula (III), R.sup.1
preferably has that meaning which has already been mentioned above,
in connection with the description of the compounds of the general
formula (I) according to the invention, as being preferred,
particularly preferred or very particularly preferred for
R.sup.1.
[0138] The starting materials of the general formula (III) are
known organic compounds.
[0139] The formula (Ia) provides a general definition of the
substituted benzoyl ketones to be used as starting materials in the
process (b) according to the invention for preparing compounds of
the general formula (I). In the general formula (Ia); n, A,
R.sup.2, R.sup.3, R.sup.4 and R.sup.11 each preferably have those
meanings which have already been mentioned above, in connection
with the description of the compounds of the general formula (I)
according to the invention, as being preferred, particularly
preferred or very particularly preferred for n, A, R.sup.2,
R.sup.3, R.sup.4 and R.sup.11.
[0140] The starting materials of the general formula (la) are novel
compounds according to the invention; they can be prepared by the
process (a) according to the invention.
[0141] The process (a) according to the invention for preparing the
novel substituted aryl ketones of the general formula (I) is, if
appropriate, carried out using a dehydrating agent. Suitable
dehydrating agents are the customary chemicals suitable for binding
water.
[0142] Examples of these which may be mentioned are
dicyclohexylcarbodiimide and carbonyldiimidazole.
[0143] A particularly suitable dehydrating agent which may be
mentioned is dicyclohexylcarbodiimide.
[0144] The process (a) according to the invention for preparing the
novel substituted aryl ketones of the general formula (I) is, if
appropriate, carried out using one or more reaction
auxiliaries.
[0145] Examples of these which may be mentioned are sodium cyanide,
potassium cyanide, acetone cyanohydrin,
2-cyano-2-(trimethylsilyloxy)-pro- pane and trimethylsilyl
cyanide.
[0146] The particularly suitable further reaction auxiliary which
may be mentioned is trimethylsilyl cyanide.
[0147] The process (a) according to the invention for preparing the
novel substituted aryl ketones of the general formula (I) is, if
appropriate, carried out using a further reaction auxiliary.
Suitable further reaction auxiliaries for the process according to
the invention are, in general, basic organic nitrogen compounds,
such as, for example, trimethylamine, triethylamine,
tripropylamine, tributylamine, ethyl-diisopropylamine,
N,N-dimethyl-cyclohexylamine, dicyclohexylamine,
ethyl-dicyclohexylamine, N,N-dimethyl-aniline,
N,N-dimethyl-benzylamine, pyridine, 2-methyl-, 3-methyl-,
4-methyl-, 2,4-dimethyl-, 2,6-dimethyl-, 3,4-dimethyl- and
3,5-dimethylpyridine, 5-ethyl-2-methyl-pyridine,
4-dimethylamino-pyridine- , N-methyl-piperidine,
1,4-diazabicyclo[2.2.2]-octane (DABCO),
1,5-diazabicyclo[4.3.0]-non-5-ene (DBN), or
1,8-diazabicyclo[5.4.0]-undec- -7-ene (DBU).
[0148] The process (b) according to the invention for preparing the
compounds of the formula (I) is, if appropriate, carried out using
orthoformic esters or N,N-dimethylformamide acetals. These
compounds preferably contain alkyl groups having 1 to 4 carbon
atoms, in particular methyl or ethyl. Examples which may be
mentioned are trimethyl orthoformate, triethyl orthoformate,
N,N-dimethyl-formamide dimethyl acetal and N,N-dimethyl-formamide
diethylacetal.
[0149] The process (b) according to the invention for preparing
compounds of the formula (I) is, if appropriate, carried out using
cyanoformic esters. These compounds preferably contain alkyl groups
having 1 to 4 carbon atoms, in particular methyl or ethyl. The
examples which may be mentioned are methyl cyanoformate and ethyl
cyanoformate.
[0150] The process (b) according to the invention for preparing
compounds of the formula (I) is, if appropriate, carried out using
(carbon disulphide and) alkylating agents. These compounds
preferably contain alkyl groups having 1 to 4 carbon atoms, in
particular methyl or ethyl. Examples which may be mentioned are
methyl chloride, methyl bromide, methyl iodide, dimethyl sulphate,
ethyl chloride, ethyl bromide, ethyl iodide and diethyl
sulphate.
[0151] The process (b) according to the invention for preparing
compounds of the formula (I) is carried using hydroxylamine or an
acid adduct thereof. Hydroxylamine hydrochloride may be mentioned
as preferred acid adduct.
[0152] The processes according to the invention for preparing the
compounds of the general formula (I) are preferably carried out
using diluents. Suitable diluents for carrying out the processes
(a) and (b) according to the invention are especially inert organic
solvents. These include, in particular, aliphatic, alicyclic or
aromatic, optionally halogenated hydrocarbons, such as, for
example, benzine, benzene, toluene, xylene, chlorobenzene,
dichlorobenzene, petroleum ether, hexane, cyclohexane,
dichloromethane, chloroform, carbon tetrachloride; ethers, such as
diethylether, diisopropylether, dioxane, tetrahydrofuran or
ethylene glycol dimethyl ether or ethylene glycol diethyl ether;
ketones, such as acetone, butanone or methyl isobutyl ketone;
nitriles, such as acetonitrile, propionitrile or butyronitrile;
amides, such as N,N-dimethylformamide, N,N-dimethylacetamide,
N-methyl-formanilide, N-methylpyrrolidone or hexamethylphosphoric
triamide; esters, such as methyl acetate or ethyl acetate;
sulphoxides, such as dimethylsulphoxide; alcohols, such as
methanol, ethanol, n- or i-propanol, ethylene glycol monomethyl
ether, ethylene glycol monoethyl ether, diethylene glycol
monomethyl ether, diethylene glycol monoethyl ether.
[0153] When carrying out the processes (a) and (b) according to the
invention, the reaction temperatures can be varied within a
relatively wide range. In general, the processes are carried out at
temperatures between 0.degree. C. and 150.degree. C., preferably
between 10.degree. C. and 120.degree. C.
[0154] The processes (a) and (b) according to the invention are
generally carried out under atmospheric pressure. However, it is
also possible to carry out the processes according to the invention
under elevated or reduced pressure--in general between 0.1 bar and
10 bar.
[0155] For carrying out the processes (a) and (b) according to the
invention, the starting materials are generally employed in
approximately equimolar amounts. However, it is also possible to
use a relatively large excess of one of the components. The
reaction is generally carried out in a suitable diluent and the
reaction mixture is generally stirred at the required temperature
for several hours. Work-up is carried out by customary methods (cf.
the Preparation Examples).
[0156] The compounds of the formulae (IV), (V), (VI), (VII) and
(VIII) to be used as starting materials in the process according to
the invention for preparing compounds of the general formula (II)
are known organic compounds.
[0157] The active compounds according to the invention can be used
as defoliants, desiccants, haulm killers and, especially, as weed
killers. Weeds in the broadest sense are understood to mean 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.
[0158] The active compounds according to the invention can be used,
for example, in connection with the following plants:
[0159] Dicotyledonous weeds of the genera: Abutilon, Amaranthus,
Ambrosia, Anoda, Anthemis, Aphanes, Atriplex, Bellis, Bidens,
Capsella, Carduus, Cassia, Centaurea, Chenopodium, Cirsium,
Convolvulus, Datura, Desmodium, Emex, Erysimum, Euphorbia,
Galeopsis, Galinsoga, Galium, Hibiscus, Ipomoea, Kochia, Lamium,
Lepidium, Lindemia, Matricaria, Mentha, Mercurialis, Mullugo,
Myosotis, Papaver, Pharbitis, Plantago, Polygonum, Portulaca,
Ranunculus, Raphanus, Rorippa, Rotala, Rumex, Salsola, Senecio,
Sesbania, Sida, Sinapis, Solanum, Sonchus, Sphenoclea, Stellaria,
Taraxacum, Thlaspi, Trifolium, Urtica, Veronica, Viola,
Xanthium.
[0160] Dicotyledonous crops of the genera: Arachis, Beta, Brassica,
Cucumis, Cucurbita, Helianthus, Daucus, Glycine, Gossypium,
Ipomoea, Lactuca, Linum, Lycopersicon, Nicotiana, Phaseolus, Pisum,
Solanum, Vicia.
[0161] Monocotyledonous weeds of the genera: Aegilops, Agropyron,
Agrostis, Alopecurus, Apera, Avena, Brachiaria, Bromus, Cenchrus,
Commelina, Cynodon, Cyperus, Dactyloctenium, Digitaria,
Echinochloa, Eleochanis, Eleusine, Eragrostis, Eriochloa, Festuca,
Fimbristylis, Heteranthera, Imperata, Ischaemum, Leptochloa,
Lolium, Monochoria, Panicum, Paspalum, Phalaris, Phleum, Poa,
Rottboellia, Sagittaria, Scirpus, Setaria, Sorghum.
[0162] Monocotyledonous crops of the genera: Allium, Ananas,
Asparagus, Avena, Hordeum, Oryza, Panicum, Saccharum, Secale,
Sorghum, Triticale, Triticum, Zea.
[0163] However, the use of the active compounds according to the
invention is in no way restricted to these genera, but also extends
in the same manner to other plants.
[0164] The active compounds according to the invention are
suitable, depending on the concentration, for the total control of
weeds, for example on industrial terrain and rail tracks, and on
paths and areas with and without tree plantings. Similarly; the
active compounds according to the invention can be employed for
controlling weeds in perennial crops, 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 hop fields, on lawns, turf and pastureland, and
for the selective control of weeds in annual crops.
[0165] The compounds of the formula (I) according to the invention
have strong herbicidal activity and a broad active spectrum when
used on the soil and on above-ground parts of plants. To a certain
extent they are also suitable for the selective control of
monocotyledonous and dicotyledonous weeds in monocotyledonous and
dicotyledononscrops, both by the pre-emergence and by the
post-emergence method.
[0166] At certain concentrations or application rates, the active
compounds according to the invention can also be employed for
controlling animal pests and fungal or bacterial plant diseases. If
appropriate, they can also be used as intermediates or precursors
for the synthesis of other active compounds.
[0167] According to the invention, it is possible to treat all
plants and parts of plants. Plants are to be understood here as
meaning 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, fruit-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.
[0168] 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.
[0169] The active compounds can be converted into the customary
formulations, such as solutions, emulsions, wettable powders,
suspensions, powders, dusts, pastes, soluble powders, granules,
suspo-emulsion concentrates, natural and synthetic substances
impregnated with active compound, and microencapsulations in
polymeric substances.
[0170] These formulations are produced in a known manner, for
example by mixing the active compounds with extenders, that is to
say liquid solvents and/or solid carriers, optionally with the use
of surfactants, that is to say emulsifiers and/or dispersants
and/or foam-formers.
[0171] If the extender used is water, it is also possible to use,
for example, organic solvents as auxiliary solvents. Liquid
solvents which are mainly suitable are: aromatics, such as xylene,
toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated
aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or
methylene chloride, aliphatic hydrocarbons, such as cyclohexane or
paraffins, for example petroleum fractions, mineral and vegetable
oils, alcohols, such as butanol or glycol, and also their ethers
and esters, ketones, such as acetone, methyl ethyl ketone, methyl
isobutyl ketone or cyclohexanone, strongly polar solvents, such as
dimethylformamide and dimethyl sulphoxide, and water.
[0172] Suitable solid carriers are: for example ammonium salts and
ground natural minerals, such as kaolins, clays, talc, chalk,
quartz, attapulgite, montmorillonite or diatomaceous earth, and
ground synthetic minerals, such as finely divided silica, alumina
and silicates; suitable solid carriers for granules are: for
example crushed and fractionated natural rocks, such as calcite,
marble, pumice, sepiolite, dolomite and synthetic granules of
inorganic and organic meals, and granules of organic material, such
as sawdust, coconut shells, maize cobs and tobacco stalks; suitable
emulsifiers and/or foam formers are: for example nonionic and
anionic emulsifiers, such as polyoxyethylene fatty acid esters,
polyoxyethylene fatty alcohol ethers, for example alkylaryl
polyglycol ethers, alkylsulphonates, alkyl sulphates,
arylsulphonates and protein hydrolysates; suitable dispersants are:
for example lignosulphite waste liquors and methylcellulose.
[0173] Tackifiers, such as carboxylmethylcellulose, natural and
synthetic polymers in the form of powders, granules or latices,
such as gum arabic, polyvinyl alcohol and polyvinyl acetate, and
also natural phospholipids, such as cephalins and lecithins, and
synthetic phospholipids can be used in the formulations. Other
possible additives are mineral and vegetable oils.
[0174] It is possible to use colorants, such as inorganic pigments,
for example iron oxide, titanium oxide, 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.
[0175] The formulations generally comprise between 0.1 and 95 per
cent by weight of active compound, preferably between 0.5 and
90%.
[0176] For controlling weeds, the active compounds according to the
invention, as such or in their formulations, can also be used as
mixtures with known herbicides and/or substances which improve the
compatibility with crop plants ("safeners"), finished formulations
or tank mixes being possible. Also possible are mixtures with
weed-killers comprising one or more known herbicides and a
safener.
[0177] Possible components for the mixtures are known herbicides,
for example acetochlor, acifluorfen (-sodium), aclonifen, alachlor,
alloxydim (-sodium), ametryne, amicarbazone, amidochlor,
amidosulphuron, anilofos, asulam, atrazine, azafenidin,
azimsulphuron, BAS-662H, beflubutamid, benazolin (-ethyl),
benfuresate, bensulphuron (-methyl), bentazon, benzfendizone,
benzobicyclon, benzofenap, benzoylprop (-ethyl), bialaphos,
bifenox, bispyribac (-sodium), bromobutide, bromofenoxim,
bromoxynil, butachlor, butafenacil (-allyl), butroxydim, butylate,
cafenstrole, caloxydim, carbetamide, carfentrazone (-ethyl),
chlomethoxyfen, chloramben, chlondazon, chlonmuron (-ethyl),
chlomitrofen, chlorsulphuron, chlortoluron, cinidon (-ethyl),
cinmethylin, cinosulphuron, clefoxydim, clethodim, clodinafop
(-propargyl), clomazone, clomeprop, clopyralid, clopyrasulphuron
(-methyl), cloransulam (-methyl), cumyluron, cyanazine, cybutryne,
cycloate, cyclosulphamuron, cycloxydim, cyhalofop (-butyl), 2,4-D,
2,4-DB, desmedipham, diallate, dicamba, dichlorprop (--P), diclofop
(-methyl), diclosulam, diethatyl (-ethyl), difenzoquat,
diflufenican, diflufenzopyr, dimefuron, dimepiperate, dimethachlor,
dimethametryn, dimethenamid, dimexyflam, dinitramine, diphenamid,
diquat, dithiopyr, diuron, dymron, epropodan, EPTC, esprocarb,
ethalfluralin, ethametsulphuron (-methyl), ethofumesate, ethoxyfen,
ethoxysulphuron, etobenzanid, fenoxaprop (--P-ethyl), fentrazamide,
flamprop (-isopropyl, -isopropyl-L, -methyl), flazasulphuron,
florasulam, fluazifop (--P-butyl), fluazolate, flucarbazone
(-sodium), flufenacet, flumetsulam, flumiclorac (-pentyl),
flumioxazin, flumipropyn, flumetsulam, fluometuron,
fluorochloridone, fluoroglycofen (-ethyl), flupox am, flupropacil,
flurpyrsulphuron (-methyl, -sodium), flurenol (-butyl), fluridone,
fluroxypyr (-butoxypropyl, -meptyl), flurprimidol, flurtamone,
fluthiacet (-methyl), fluthiamide, fomesafen, foramsulphuron,
glufosinate (-ammonium), glyphosate (-isopropylammonium),
halosafen, haloxyfop (-ethoxyethyl, --P-methyl), hexazinone,
imazamethabenz (-methyl), imazamethapyr, imazamox, imazapic,
imazapyr, imazaquin, imazethapyr, imazosulphuron, iodosulphuron
(-methyl, -sodium), ioxynil, isopropalin, isoproturon, isouron,
isoxaben, isoxachlortole, isoxaflutole, isoxapyrifop, lactofen,
lenacil, linuron, MCPA, mecoprop, mefenacet, mesosulphuron,
mesotnione, metamitron, metazachlor, methabenzthiazuron,
metobenzuron, metobromuron, (alpha-) metolachlor, metosulam,
metoxuron, metribuzin, metsulphuron (-methyl), molinate,
monolinuron, naproanilide, napropamide, neburon, nicosulphuron,
norflurazon, orbencarb, oryzalin, oxadiargyl, oxadiazon,
oxasulphuron, oxaziclomefone, oxyfluorfen, paraquat, pelargon acid,
pendimethalin, pendralin, pentoxazone, phenmedipham, picolinafen,
piperophos, pretilachlor, pnimisulphuron (-methyl), profluazol,
prometryn, propachlor, propanil, propaquizafop, propisochlor,
procarbazone (-sodium), propyzamide, prosulphocarb, prosulphuron,
pyraflufen (-ethyl), pyrazogyl, pyrazolate, pyrazosulphuron
(-ethyl), pyrazoxyfen, pyribenzoxim, pyributicarb, pyridate,
pynidatol, pyriftalid, pyriminobac (-methyl), pyrithiobac
(-sodium), quinchlorac, quinmerac, quinoclamine, quizalofop
(--P-ethyl, --P-tefuryl), rimsulphuron, sethoxydim, simazine,
simetryn, sulcotnione, sulphentrazone, sulphometuron (-methyl),
sulphosate, sulphosulphuron, tebutam, tebuthiuron, tepraloxydim,
terbuthylazine, terbutryn, thenylchlor, thiafluamide, thiazopyr,
thidiazimin, thifensulphuron (-methyl), thiobencarb, tiocarbazil,
tralkoxydim, triallate, triasulphuron, tribenuron (-methyl),
itnclopyr, tridiphane, trifluralin, tnfloxysulphuron,
tnflusulphuron (-methyl), tritosulphuron.
[0178] A mixture with other known active compounds, such as
fungicides, insecticides, acaricides, nematicides, bird repellents,
plant nutrients and agents which improve soil structure, is also
possible.
[0179] The active compounds can be used as such, in the form of
their formulations or in the use forms prepared therefrom by
further dilution, such as ready-to-use solutions, suspensions,
emulsions, powders, pastes and granules. They are used in a
customary manner, for example by watering, spraying, atomizing or
broadcasting.
[0180] The active compounds according to the invention can be
applied both before and after emergence of the plants. They can
also be incorporated into the soil before sowing.
[0181] The amount of active compound used can vary within a
relatively wide range. It depends essentially on the nature of the
desired effect. In general, the amounts used are between 1 g and 10
kg of active compound per hectare of soil surface, preferably
between 5 g and 5 kg per ha.
[0182] The preparation and the use of the active compounds
according to the invention is illustrated by the examples
below.
PREPARATION EXAMPLES
EXAMPLE 1
[0183] 20
[0184] (Process (a))
[0185] 0.30 g of (2.7 mmol) of 1-ethyl-5-hydroxy-pyrazole, 0.8 g
(8.0 mmol) of triethylamine and a drop of N,N-dimethyl-formamide
are added successively to a solution of 1.1 g (2.7 mmol) of
3-[2-(3',4'-dimethyl-1'-
,2',4'-1H-triazolin-5'-on-1'-yl)-ethoxy]-2-methyl-4-methylsulphonyl-benzoy-
l chloride in 20 ml of dichloromethane. The mixture is stirred at
room temperature (about 20.degree. C.), for about 24 hours, the
reaction solution is washed successively with 1N hydrochloric acid
and saturated sodium chloride solution and dried over magnesium
sulphate and the solvent is removed under water pump vacuum. The
residue is dissolved in 30 ml of acetonitrile and, with slight
cooling, admixed successively with 0.28 g (3.3 mmol) of
2-hydroxyl-2-methylpropionitrile and 1.4 g (14 mmol) of
triethylamine. The mixture is stirred at room temperature for
another 24 hours, the major part of the solvent is removed under
water pump vacuum and the residue is dissolved in dichloromethane
and 1N hydrochloric acid. The organic-phase is separated off,
washed with water and saturated sodium chloride solution, dried
over magnesium sulphate and filtered. From the filtrate, the
solvent is carefully distilled off under reduced pressure.
[0186] This gives 1.1 g (88% of theory) of
4-{3-[2-(3',4'-dimethyl-1',2',4-
'-1H-triazolin-5'-on-1'-yl)-ethyloxy]-2-methyl-4-methylsulphonyl-benzoyl}--
1-ethyl-5-hydroxy-1H-pyrazole as an oily residue.
[0187] Log P: 1.23.
EXAMPLE 2
[0188] 21
[0189] 1.95 g (5.4 mmol) of
3-(3'-ethoxy-4'-methyl-1',2',4'-1H-triazolin-5-
'-on-1'-yl)-methoxy-2,4-dichloro-benzoic acid are dissolved in 75
ml of acetonitrile and mixed with 0.61 g of 1,3-cyclohexanedione
(5.4 mmol) and 1.33 g of dicyclohexylcarbodiimide (DCC, 1.2
equivalents). The mixture is stirred at room temperature (about
20.degree. C.) for 15 hours, and 1.5 ml of triethylamine (2
equivalents) and 0.29 ml of trimethylsilyl cyanide (0.4
equivalents) are then added. After 2 hours at room temperature, the
mixture is concentrated under water pump vacuum and the residue is
stirred with 10% strength aqueous sodium carbonate solution and
filtered off. The filtrate is shaken with diethylether and the
aqueous phase is acidified with 2N hydrochloric acid. The
precipitated product is extracted repeatedly with dichloromethane
and the combined organic phases are dried over sodium sulphate,
filtered and concentrated.
[0190] This gives 1.3 g (53% of theory) of
2-[3-(3'-ethoxy-4'-methyl-1',2'-
,4'-1H-triazolin-5'-on-1'-yl)-methoxy-2,4-dichloro-benzoyl]-1,3-cyclohexan-
edione as a viscous resin.
[0191] LogP 2.52.
[0192] Analogously to Examples 1 and 2, and in accordance with the
general description of the preparation processes according to the
invention, it is also possible to prepare, for example, the
compounds of the general formula (I) listed in Table I below.
1TABLE 1 Examples of the compounds of the formula (I) (I) 22
(position Ex. (position) (position) OAR.sup.4) No. A R.sup.1
R.sup.2 (R.sup.3)n R.sup.4 Physical data 3 CH.sub.2 23 (2) Cl (4)
Cl 24 logP = 2.04.sup.a) 4 CH.sub.2CH.sub.2 25 (2) Cl (4) Cl 26
logP = 1.92.sup.a) 5 CH.sub.2CH.sub.2 27 (2) Cl (4) Cl 28 logP =
1.52.sup.a) 6 CH.sub.2CH.sub.2 29 (2) CH.sub.3 (4) Cl 30 logP =
1.93.sup.a) 7 CH.sub.2CH.sub.2 31 (2) CH.sub.3 (4) Cl 32 logP =
1.68.sup.a) 8 CH.sub.2CH.sub.2 33 (2) Cl (4) SCH.sub.3 34 logP =
1.94.sup.a) 9 CH.sub.2CH.sub.2 35 (2) Cl (4) SCH.sub.3 36 logP =
1.58.sup.a) 10 CH.sub.2CH.sub.2 37 (2) CH.sub.3 (4) SCH.sub.3 38
logP = 1.91.sup.a) 11 CH.sub.2CH.sub.2 39 (2) Cl (4)
SO.sub.2CH.sub.3 40 logP = 1.65.sup.a) 12 CH.sub.2CH.sub.2 41 (2)
CH.sub.3 (4) Cl 42 logP = 2.07.sup.a) 13 CH.sub.2 43 (2) Cl (4) Cl
44 logP = 2.44.sup.a) 14 CH.sub.2CH.sub.2 45 (2) Cl (4) SCH.sub.3
46 logP = 2.05.sup.a) 15 CH.sub.2CH.sub.2 47 (2) Cl (4) Cl 48 logP
= 1.69.sup.a) 16 CH.sub.2CH.sub.2 49 (2) Cl (4) Cl 50 logP =
1.92.sup.a) 17 CH.sub.2CH.sub.2 51 (2) Cl (4) Cl 52 logP =
1.93.sup.a) 18 CH.sub.2CH.sub.2 53 (2) Cl (4) Cl 54 logP =
1.62.sup.a) 19 CH.sub.2CH.sub.2 55 (2) Cl (4) Cl 56 logP =
2.06.sup.a) 20 CH.sub.2 57 (2) Cl (4) SCH.sub.3 58 (S enantiomer
logP = 1.60.sup.a) 21 CH.sub.2CH.sub.2 59 (2) Cl (4) Cl 60 logP =
2.39.sup.a) 22 CH.sub.2CH.sub.2 61 (2) Cl (4) Cl 62 logP =
2.16.sup.a) 23 CH.sub.2CH.sub.2 63 (2) Cl (4) Cl 64 logP =
2.40.sup.a) 24 CH.sub.2 65 (2) Cl (4) SCH.sub.3 66 (S enantiomer
logP = 1.98.sup.a) 25 CH.sub.2CH.sub.2 67 (2) CH.sub.3 (4) Cl 68
logP = 1.88.sup.a) 26 CH.sub.2CH.sub.2 69 (2) CH.sub.3 (4) Cl 70
logP = 2.15.sup.a) 27 CH.sub.2CH.sub.2 71 (2) CH.sub.3 (4) Cl 72
logP = 2.11.sup.a) 28 CH.sub.2CH.sub.2 73 (2) CH.sub.3 (4) Cl 74
logP = 2.38.sup.a) 29 CH.sub.2CH.sub.2 75 (2) CH.sub.3 (4) Cl 76
logP = 2.12.sup.a) 30 CH.sub.2CH.sub.2 77 (2) CH.sub.3 (4) Cl 78
logP = 1.78.sup.a) 31 CH.sub.2CH.sub.2 79 (2) CH.sub.3 (4) Cl 80
logP = 2.38.sup.a) 32 CH.sub.2CH.sub.2 81 (2) CH.sub.3 (4) Cl 82
logP = 2.04.sup.a) 33 CH.sub.2CH.sub.2 83 (2) CH.sub.3 (4)
SCH.sub.3 84 logP = 1.97.sup.a) 34 CH.sub.2CH.sub.2 85 (2) Cl (4)
SCH.sub.3 86 logP = 2.36.sup.a) 35 CH.sub.2 87 (2) CH.sub.3 (4) Cl
88 (S enantiomer) [.alpha.].sub.D.sup.20 = +2.3 logP = 1.67.sup.a)
36 CH.sub.2 89 (2) CH.sub.3 (4) Cl 90 (S enantiomer) logP =
1.94.sup.a) 37 CH.sub.2 91 (2) CH.sub.3 (4) Cl 92 (S enantiomer)
logP = 1.85.sup.a) 38 CH.sub.2 93 (2) CH.sub.3 (4) Cl 94 (S
enantiomer) logP = 2.10.sup.a) 39 CH.sub.2 95 (2) Cl (4) Cl 96 (S
enantiomer) logP = 2.12.sup.a) 40 CH.sub.2 97 (2) Cl (4) Cl 98 (S
enantiomer) logP = 1.67.sup.a) 41 CH.sub.2 99 (2) Cl -- 100 (S
enantiomer) logP = 2.42.sup.a) 42 CH.sub.2 101 (4) Cl -- 102 (S
enantiomer) logP = 1.65.sup.a) 43 CH.sub.2CH.sub.2 103 (2) Cl (4)
SCH.sub.3 104 44 CH.sub.2CH.sub.2 105 (2) Cl (4) SCH.sub.3 106 logP
= 2.05.sup.a) 45 CH.sub.2 107 (2) Cl (4) SCH.sub.3 108 (S
enantiomer) logP = 2.68.sup.a) 46 CH.sub.2 109 (2) Cl (4) SCH.sub.3
110 (S enantiomer) logP = 2.13.sup.a) 47 CH.sub.2 111 (2) Cl (4) Cl
112 (S enantiomer) logP = 1.95.sup.a) 48 CH.sub.2 113 (2) Cl (4) Cl
114 (S enantiomer) logP = 1.51.sup.a) 49 CH.sub.2 115 (2) Cl -- 116
logP = 1.92.sup.a) 50 CH.sub.2CH.sub.2 117 (2) Br (4) Br 118
n.sub.D.sup.20 = 1.5970 51 CH.sub.2CH.sub.2 119 (2) Cl (4) Cl 120
n.sub.D.sup.20 = 1.5825 52 CH.sub.2CH.sub.2 121 (2) Cl (4) Cl 122
n.sub.D.sup.20 = 1.5790 53 CH.sub.2CH.sub.2 123 (2) Cl (4)
SO.sub.2CH.sub.3 124 m.p.: 69.degree. C. 54 CH.sub.2CH.sub.2 125
(2) Cl (4) SO.sub.2CH.sub.3 126 m.p.: 62.degree. C. 55 CH.sub.2 127
(4) CF.sub.3 -- 128 56 CH.sub.2 129 (4) CF.sub.3 -- 130 57 CH.sub.2
131 (4) CF.sub.3 -- 132 58 CH.sub.2 133 (4) CF.sub.3 -- 134 59
CH.sub.2 135 (2) Br (4) Br 136 (S enantiomer) 60 CH.sub.2 137 (2)
Br (4) Br 138 (S enantiomer) logP = 1.56.sup.a) 61 CH.sub.2 139 (2)
Br (4) Br 140 (S enantiomer) logP = 2.02.sup.a)
[0193] The log P values given in Table 1 were determined in
accordance with EEC Directive 79/831 V.A8 by HPLC (High Performance
Liquid Chromatography) on a reversed-phase column (C 18).
Temperature: 43.degree. C.
[0194] (a) Mobile phases for the determination in the acidic range:
0.1% aqueous phosphoric acid, acetonitrile; linear gradient of 10%
acetonitrile to 90% acetonitrile--the corresponding data in Table 1
are labelled.sup.a).
[0195] (b) Mobile phases for the determination in the neutral
range: 0.01 molar aqueous phosphate buffer solution, acetonitnile,
linear gradient from 10% acetonitrile to 90% acetonitnile--the
corresponding data in Table 1 are labelled.sup.b).
[0196] Calibration was carried out using unbranched alkan-2-ones
(with 3 to 16 carbon atoms) whose log P values are known
(determination of the log P values by the retention times using
linear interpolation between two successive alkanones).
[0197] The lambda-max values were determined in the maxima of the
chromatographic signals using UV spectra from 200 nm to 400 nm.
[0198] Starting Materials of the Formula (II):
EXAMPLE (II-1)
[0199] 141
[0200] Step 1 142
[0201] Over a period of 4 to 6 hours, 43 g (0.606 mol) of chlorine
gas are introduced into a boiling solution of 100 g (0.6 mol) of
methyl 3-hydroxy-2-methyl-benzoate and 0.4 ml of diisopropylamine
in 800 ml of 1,2-dichloro-ethane. After cooling, the solution is
washed successively with in each case 200 ml of 5% strength sodium
hydrogen sulphite solution and with saturated sodium chloride
solution, the organic phase is dried over magnesium sulphate and
the solvent is removed under water pump vacuum. The dark-brown oil
obtained as the residue is admixed with 30 ml of diethyl ether and
cooled to from 0.degree. to 4.degree. C. for crystallization. The
precipitated crystals are isolated by filtration with suction,
washed with a little cold diethyl ether and dried under reduced
pressure at 30.degree. C.
[0202] This gives 46.6 g (39% of theory) of methyl
4-chloro-3-hydroxy-2-me- thylbenzoate.
[0203] LogP: 2.14.
[0204] Using, instead of methyl 3-hydroxy-2-methyl-benzoate, the
corresponding ethyl ester, ethyl
4-chloro-3-hydroxy-2-methyl-benzoate is obtained by the same
process.
[0205] Melting point: 51.degree. C.
[0206] Step 2 143
[0207] A solution of 25 g (0.125 mol) of methyl
4-chloro-3-hydroxy-2-methy- l-benzoate in 400 ml of acetonitrile is
admixed successively with 34.2 g (0.248 mol) of powdered anhydrous
potassium carbonate and 29.3 g (0.125 mol) of
2-chloro-ethanol-p-toluene sulphonate. The reaction mixture is
heated at 70.degree. C. for about 7 hours and then allowed to cool,
and the major part of the solvent is removed under water pump
vacuum. The residue is dissolved in 200 ml of dichloromethane and
300 ml of water. The organic phase is separated off, washed with
water, dried over magnesium sulphate and filtered. From the
filtrate, the solvent is carefully distilled off under reduced
pressure.
[0208] This gives 32.5 g (99% of theory) of methyl
4-chloro-3-(2-chloro-et- hoxy)-2-methyl-benzoate as a dark oil.
[0209] Log P=3.52.
[0210] Step 3 144
[0211] A solution of 16.0 g (60.8 mmol) of methyl
4-chloro-3-(2-chloro-eth- oxy)-2-methyl-benzoate in 70 ml of
dimethyl sulphoxide is admixed successively with 18.4 g (0.133 mol)
of powdered anhydrous potassium carbonate and 6.9 g (60.8 mmol) of
3,4-dimethyl-1,2,4-triazolin-5-one. The reaction mixture is heated
at 90.degree. C., for about 6 hours and then allowed to cool, and
the major part of the solvent is removed under water pump vacuum.
The residue is dissolved in 140 ml of dichloromethane and 60 ml of
water. The organic phase is separated off, washed with water, dried
over magnesium sulphate and concentrated under water pump vacuum.
The oily residue is stirred with 25 ml of petroleum ether. The
resulting crystalline product is isolated by filtration with
suction.
[0212] This gives 18.5 g (80% of theory) of methyl
4-chloro-3-[2-(3',4'-di-
methyl-1',2',4'-1H-triazolin-5'-on-1'-yl)-ethoxy]-2-methyl-benzoate.
[0213] Log P: 1.94.
EXAMPLE (II-2)
[0214] 145
[0215] With ice-cooling, 3.3 g (44.5 mmol) of sodium methyl
mercaptide are added to a solution of 12.4 g (36.5 mmol) of methyl
4-chloro-3-[2-(3',4'-dimethyl-1',2',4'-1H-triazolin-5'-on-1'-yl)-ethoxy]--
2-methyl-benzoate in 100 ml of N,N-dimethylformamide. The mixture
is stirred at room temperature (about 20.degree. C.) for about 6
hours, and the major part of the solvent is removed under water
pump vacuum. The residue is dissolved in 300 ml of ethyl acetate
and 200 ml of water. The organic phase is separated off, washed
with water, dried over magnesium sulphate and filtered. From the
filtrate, the solvent is carefully distilled off under reduced
pressure.
[0216] This gives 5.4 g (42% of theory) of methyl
3-[2-(3',4'-dimethyl-1',-
2',4'-1H-triazolin-5'-on-1'-yl)-ethoxyl-2-methyl-4-methylthio-benzoate.
[0217] LogP=1.89.
EXAMPLE (II-3)
[0218] 146
[0219] 10 mg of ammonium molybdate tetrahydrate and 17.3 g (178
mmol) of a 35% strength aqueous hydrogen peroxide solution are
added to a solution of 12.3 g (33.7 mmol) of ethyl
3-[2-(3',4'-dimethyl-1',2',4'-1H-triazolin-
-5'-on-1'-yl)-ethoxy]-2-methyl-4-methylthio-benzoate in 40 ml of
acetic acid. The reaction mixture is heated at from 50.degree. to
60.degree. C. for about 6 hours, diluted with water and extracted
with ethyl acetate. The organic phase is separated off, washed
successively with water, sodium bicarbonate solution, sodium
thiosulphate solution and again with water, dried over magnesium
sulphate and filtered. From the filtrate, the solvent is carefully
distilled off under reduced pressure.
[0220] This gives 12.3 g (92% of theory) of ethyl
3-[2-(3',4'-dimethyl-1',-
2',4'-1H-triazolin-5'-on-1'-yl)-ethoxy]-2-methyl4-methylsulphonyl-benzoate-
.
[0221] LogP=1.76.
EXAMPLE (II-4)
[0222] 147
[0223] 1.2 g (30 mmol) of a solution of sodium hydroxide in 20 ml
of water are added to a solution of 6.5 g (19.0 mmol) of methyl
4-chloro-3-[2-(3',4'-dimethyl-1',2',4'-1H-triazolin-5'-on-1'-yl)-ethoxy]--
2-methyl-benzoate in 40 ml of ethanol. The solution is stirred at
room temperature (about 20.degree. C.) for about 24 hours, and the
major part of the solvent is removed under water pump vacuum. The
residue is dissolved in water and acidified with hydrochloric acid.
The resulting suspension is extracted with ethyl acetate and the
organic phase is separated off, washed with saturated sodium
chloride solution, dried over magnesium sulphate and filtered. From
the filtrate the solvent is carefully distilled off under reduced
pressure.
[0224] This gives 5.9 g (95% of theory) of
4-chloro-3-[2-(3',4'-dimethyl-1-
',2',4'-1H-triazolin-5'-on-1'-yl)-ethoxyl-2-methyl-benzoic
acid.
[0225] Log P=1.37.
EXAMPLE (II-5)
[0226] 148
[0227] 2.3 g (6.65 mmol) of
2,4-dichloro-3-[2-(3',4'-dimethyl-1',2',4'-1H--
triazolin-5'-on-1'-yl)-ethoxy]-2-benzoic acid in 10 ml of thionyl
chloride are heated at 70.degree. C. for about 1.5 hours. The
reaction solution is allowed to cool and the excess thionyl
chloride is removed under reduced pressure.
[0228] This gives 2.4 g (100% of theory) of
2,4-dichloro-3-[2-(3',4'-dimet-
hyl-1',2',4'-1H-triazolin-5'-on-1'-yl)-ethoxy]-2-benzoyl
chloride.
[0229] Log P=1.24.
EXAMPLE (II-6)
[0230] 149
[0231] 5 g (21.3 mmol) of ethyl 2,4-dichloro-3-hydroxy-benzoate are
dissolved in 200 ml of tetrahydrofuran and admixed with 3.68 g
(21.3 mmol) of
1'-hydroxymethyl-3-ethoxy-4-methyl-1,2,4-triazolin-5-one. 5.58 g
(21.3 mmol) of triphenylphosphine are added, and at 0.degree. C.,
4.4 g of 85% diethyl diazo-dicarbbxylate are then added dropwise.
The resulting solution is stirred overnight, concentrated under
water pump vacuum and filtered through silica gel (ethyl
acetate/hexane). The filtrate is concentrated and mixed with
diethyl ether. The solid that separates off is filtered off, and
the solvent is carefully distilled off from the filtrate under
reduced pressure.
[0232] This gives 6.8 g (82% of theory) of ethyl
3-(3'-ethoxy-4'-methyl-1'-
,2',4'-1H-triazolin-5'-on-1'-yl)-methoxy-2,4-dichloro-benzoate as a
viscous oil.
[0233] Log P=2.77.
EXAMPLE (II-7)
[0234] 150
[0235] 2 g (8.5 mmol) of ethyl 2,4-dichloro-3-hydroxy-benzoate are
dissolved in 30 ml of acetonitrile and mixed successively with 0.86
g (8.5 mmol) of triethylamine and 1.2 g (8.5 mmol) of
N-chloromethyl-2-pyridone. The resulting mixture is stirred at
60.degree. C. for 7 hours, admixed with water and extracted with
ethyl acetate. The organic phase is separated off, washed with
saturated sodium chloride solution, dried over magnesium sulphate
and filtered. The solvent is carefully distilled off under reduced
pressure.
[0236] This gives 2.4 g (82% of theory) of ethyl
2,4-dichloro-3-(1H-pyrid-- 2-on-1-yl)-methoxy-benzoate.
EXAMPLE (II-8)
[0237] 151
[0238] 6.4 g (16.3 mmol) of ethyl 3-
(3'-ethoxy-4'-methyl-1',2',4'-1H-tria-
zolin-5'-on-1'-yl)-methoxy-2,4-dichloro-benzoate are stirred in a
mixture of 250 ml of cyclohexane and 25 ml of ethylene glycol
monomethyl ether in the presence of 0.91 g of powdered potassium
hydroxide at room temperature (about 20.degree. C.) for 15 hours.
The mixture is diluted with water and acidified with 2N
hydrochloric acid. The precipitated solid is isolated by filtration
with suction.
[0239] This gives 4.05 g (69% of theory) of
3-(3'-ethoxy-4'-methyl-1',2',4-
'-1H-triazolin-5'-on-1'-yl)-methoxy-2,4-dichloro-benzoic acid.
[0240] log P: 1.74.
[0241] Analogously to Examples (II-1) to (II-8), it is also
possible to prepare, for example, the compounds of the general
formula (II) listed in Table 2 below, or reactive derivatives
thereof--cf. formula (IIA), 152
[0242] where
[0243] R has one of the meanings listed in the Table below.
2TABLE 2 Examples of compounds of the formula (II) or (IIA)
(position Ex. (position) (position) OAR.sup.4) No. A R.sup.2
(R.sup.3).sub.n R.sup.4 R Physical data II-9 CH.sub.2CH.sub.2 (2)
CH.sub.3 (4) Cl 153 C.sub.2H.sub.5 logP = 2.25.sup.a) II-10
CH.sub.2CH.sub.2 (2) CH.sub.3 (4) SCH.sub.3 154 C.sub.2H.sub.5 logP
= 2.16.sup.a) II-11 CH.sub.2CH.sub.2 (2) CH.sub.3 (4)
SO.sub.2CH.sub.3 155 CH.sub.3 logP = 1.48.sup.a) II-12
CH.sub.2CH.sub.2 (2) CH.sub.3 (4) SCH.sub.3 156 H logP =
1.33.sup.a) II-13 CH.sub.2CH.sub.2 (2) CH.sub.3 (4)
SO.sub.2CH.sub.3 157 H logP = 0.92.sup.a) II-14 CH.sub.2CH.sub.2
(2) Cl (4) Cl 158 C.sub.2H.sub.5 logP = 2.08.sup.a) II-15
CH.sub.2CH.sub.2 (2) Cl (4) Cl 159 H logP = 1.23.sup.a) II-16
CH.sub.2CH.sub.2 (2) SCH.sub.3 (4) SCH.sub.3 160 C.sub.2H.sub.5
logP = 2.13.sup.a) II-17 CH.sub.2CH.sub.2 (2) Cl (4) SCH.sub.3 161
C.sub.2H.sub.5 logP = 2.09.sup.a) II-18 CH.sub.2CH.sub.2 (2) Cl (4)
SCH.sub.3 162 H logP = 1.27.sup.a) II-19 CH.sub.2CH.sub.2 (2) Cl
(4) SOCH.sub.3 163 H logP = 0.59.sup.a) II-20 CH.sub.2CH.sub.2 (2)
Cl (4) SOCH.sub.3 164 C.sub.2H.sub.5 logP = 1.72.sup.a) II-21
CH.sub.2CH.sub.2 (2) Cl (4) SOCH.sub.3 165 H logP = 0.77.sup.a)
II-22 CH.sub.2CH.sub.2 (2) SO.sub.2CH.sub.3 (4) SO.sub.2CH.sub.3
166 H logP = 0.46.sup.a) II-23 CH.sub.2CH.sub.2 (2) Cl (4)
SO.sub.2CH.sub.3 167 C.sub.2H.sub.5 logP = 1.49.sup.a) II-24
CH.sub.2CH.sub.2 (2) CH.sub.3 (4) SO.sub.2CH.sub.3 168 H (xHCl)
logP = 0.95.sup.a) II-25 CH.sub.2CH.sub.2 (2) Cl (4)
SO.sub.2CH.sub.3 169 H (xHCl) logP = 0.83.sup.a) II-26
CH.sub.2CH.sub.2 (2) CH.sub.3 (4) SCH.sub.3 170 H (xHCl) logP =
1.34.sup.a) II-27 CH.sub.2CH.sub.2 (2) Cl (4) SCH.sub.3 171 H
(xHCl) logP = 1.27.sup.a) II-28 CH.sub.2CH.sub.2 (2) CH.sub.3 (4)
Cl 172 H (xHCl) logP = 1.37.sup.a) II-29 CH.sub.2 (2) Cl (4) Cl 173
C.sub.2H.sub.5 logP = 2.69.sup.a) II-30 CH.sub.2 (2) CH.sub.3 (4)
Cl 174 CH.sub.3 logP = 2.13.sup.a) II-31 CH.sub.2 (2) Cl (4) Cl 175
H logP = 1.68.sup.a) II-32 CH.sub.2 (2) Cl (4) Cl 176 H .sup.1H-NMR
(DMSO-D6). .delta.): 5.89 ppm (s, CH.sub.2) II-33 CH.sub.2CH.sub.2
(2) Cl (4) Cl 177 C.sub.2H.sub.5 logP = 2.40.sup.a) II-34
CH.sub.2CH.sub.2 (2) Cl (4) Cl 178 H logP = 1.52.sup.a) II-35
CH.sub.2CH.sub.2 (2) Cl (4) Cl 179 C.sub.2H.sub.5 logP =
2.66.sup.a) II-36 CH.sub.2CH.sub.2 (2) Cl (4) Cl 180 H logP =
1.72.sup.a) II-37 CH.sub.2CH.sub.2 (2) Cl (4) Cl 181 C.sub.2H.sub.5
logP = 2.68.sup.a) II-38 CH.sub.2CH.sub.2 (2) Cl (4) Cl 182 H logP
= 1.73.sup.a) II-39 CH.sub.2CH.sub.2 (2) Cl (4) Cl 183
C.sub.2H.sub.5 logP = 2.28.sup.a) II-40 CH.sub.2CH.sub.2 (2) Cl (4)
Cl 184 H logP = 1.45.sup.a) II-41 CH.sub.2CH.sub.2 (2) CH.sub.3 (4)
Cl 185 CH.sub.3 logP = 2.17.sup.a) II-42 CH.sub.2CH.sub.2 (2)
CH.sub.3 (4) Cl 186 H logP = 1.78.sup.a) II-43 CH.sub.2CH.sub.2 (2)
CH.sub.3 (4) Cl 187 CH.sub.3 logP = 2.44.sup.a) II-44
CH.sub.2CH.sub.2 (2) CH.sub.3 (4) Cl 188 H logP = 1.75.sup.a) II-45
CH.sub.2CH.sub.2 (2) CH.sub.3 (4) Cl 189 CH.sub.3 logP =
2.46.sup.a) II-46 CH.sub.2CH.sub.2 (2) CH.sub.3 (4) Cl 190 H logP =
1.79.sup.a) II-47 CH.sub.2CH.sub.2 (2) CH.sub.3 (4) Cl 191 CH.sub.3
logP = 2.06.sup.a) II-48 CH.sub.2CH.sub.2 (2) CH.sub.3 (4) Cl 192 H
logP = 1.49.sup.a) II-49 CH.sub.2CH.sub.2 (2) Cl (4) SCH.sub.3 193
C.sub.2H.sub.5 logP = 2.59.sup.a) II-50 CH.sub.2CH.sub.2 (2) Cl (4)
SCH.sub.3 194 H logP = 1.64.sup.a) II-51 CH.sub.2CH.sub.2 (2) Cl
(4) SCH.sub.3 195 C.sub.2H.sub.5 logP = 2.22.sup.a) II-52
CH.sub.2CH.sub.2 (2) Cl (4) SCH.sub.3 196 H logP = 1.37.sup.a)
II-53 CH.sub.2 (2) Cl (4) SCH.sub.3 197 C.sub.2H.sub.5 (S
enantiomer) logP = 2.17.sup.a) II-54 CH.sub.2 (2) Cl (4) SCH.sub.3
198 H (S enantiomer) logP = 1.31.sup.a) II-55 CH.sub.2 (2) Cl (4)
SCH.sub.3 199 C.sub.2H.sub.5 (S enantiomer) logP = 2.35.sup.a)
II-56 CH.sub.2 (2) Cl (4) SCH.sub.3 200 H (S enantiomer) logP =
1.44.sup.a) II-57 CH.sub.2 (2) CH.sub.3 (4) Cl 201 C.sub.2H.sub.5
(S enantiomer) logP = 1.95.sup.a) II-58 CH.sub.2 (2) CH.sub.3 (4)
Cl 202 H (S enantiomer) logP = 1.39.sup.a) II-59 CH.sub.2 (2)
CH.sub.3 (4) Cl 203 C.sub.2H.sub.5 (S enantiomer) logP =
2.18.sup.a) II-60 CH.sub.2 (2) CH.sub.3 (4) Cl 204 H (S enantiomer)
logP = 1.55.sup.a) II-61 CH.sub.2 (2) Cl (4) Cl 205 C.sub.2H.sub.5
(S enantiomer) logP = 2.15.sup.a) II-62 CH.sub.2 (2) Cl (4) Cl 206
H (S enantiomer) logP = 1.28.sup.a) II-63 CH.sub.2 (2) Cl (4) Cl
207 C.sub.2H.sub.5 (S enantiomer) II-64 CH.sub.2 (2) Cl (4) Cl 208
CH.sub.3 (S enantiomer) n.sub.D.sup.20 = -20.4 logP = 2.01.sup.a)
II-65 CH.sub.2 (2) Cl (4) Cl 209 H (S enantiomer) logP =
1.42.sup.a) II-66 CH.sub.2 (4) Cl -- 210 CH.sub.3 logP =
2.33.sup.a) II-67 CH.sub.2 (4) Cl -- 211 H logP = 1.81.sup.a) II-68
CH.sub.2 (4) Cl -- 212 CH.sub.3 logP = 2.23.sup.a) II-69 CH.sub.2
(4) Cl -- 213 CH.sub.3 logP = 2.07.sup.a) II-70 CH.sub.2 (4) Cl --
214 H logP = 1.36.sup.a) II-71 CH.sub.2 (4) CF.sub.3 -- 215
CH.sub.3 II-72 CH.sub.2 (4) CF.sub.3 -- 216 H II-73 CH.sub.2 (4)
CF.sub.3 -- 217 CH.sub.3 II-74 CH.sub.2 (4) CF.sub.3 -- 218 H II-75
CH.sub.2 (4) Br (4) Br 219 C.sub.2H.sub.5 (S enantiomer) logP =
2.20.sup.a) II-76 CH.sub.2 (4) Br (4) Br 220 C.sub.2H.sub.5 (S
enantiomer) logP = 2.46.sup.a) II-77 CH.sub.2 (4) Br (4) Br 221 H
(S enantiomer) logP = 1.34.sup.a) II-78 CH.sub.2 (4) Br (4) Br 222
H (S enantiomer) logP = 1.49.sup.a)
[0244] The compound listed in Table 2 as Example (II-35) can be
prepared, for example, as follows:
EXAMPLE (II-35)
[0245] Step 1 223
[0246] A solution of 15 g (68 mmol) of ethyl
2,4-dichloro-3-hydroxy-benzoa- te in 80 ml of
N,N-dimethyl-formamide is admixed successively with 19 g (137 mmol)
of potassium carbonate (powder), 38.6 g (205 mmol) of
12-dibromo-ethane and 0.4 g of sodium iodide. The mixture is heated
at 80.degree. C. for 2 hours and then allowed to cool to room
temperature and-shaken with 350 ml of diethyl ether. The organic
phase is washed with water, 10% strength aqueous sodium hydroxide
solution and finally with 10% strength hydrochloric acid and then
dried with sodium sulphate and filtered. From the filtrate, the
solvent is carefully distilled off under reduced pressure.
[0247] This gives 22.2 g (95% of theory) of ethyl
2,4-dichloro-3-(2-bromo-- ethoxy)-benzoate as an oily residue
(logP=3.98.sup.a)).
[0248] Step 2 224
[0249] A solution of 18 g (93 mmol) of ethyl
2,4-dichloro-3-(2-bromo-ethox- y)-benzoate in 100 ml of
N,N-dimethyl-formamide is admixed successively with 14.6 g (106
mmol) of potassium carbonate (powder), 19.3 g (133 mmol) of
3-methylthio-4-methyl-1,2,4-triazolin-5-one and 0.5 g of sodium
iodide. The mixture is heated at 80.degree. C. for 4 hours and then
cooled to room temperature and shaken with 400 ml of
dichloromethane, and the organic phase is washed with water, then
with 10% strength aqueous sodium hydroxide solution and finally
with 10% strength hydrochloric acid, then dried with sodium
sulphate and filtered. From the filtrate, the solvent is carefully
distilled off under reduced pressure.
[0250] This gives 17.7 g (82% of theory) of ethyl
2,4-dichloro-3-[2-(3-met-
hylthio-4-methyl-5-oxo-1,2,4-triazolin-1-yl)-ethoxy]-benzoate as an
oily residue (logP=2.66.sup.a)).
[0251] The compound listed in Table 2 as Example (II-61) can be
prepared, for example, as follows:
EXAMPLE (II-61)
[0252] 225
[0253] A mixture of 2.0 g (8.5 mmol) of ethyl
2,4-dichloro-3-hydroxy-benzo- ate, 3.6 g (12.75 mmol) of
(S)-(+)-5-(p-tolylsulphonyloxymethyl)-pyrrolidi- n-2-one, 2.3 g (17
mmol) of potassium carbonate and 30 ml of acetonitrile is stirred
at 76.degree. C. for 13 hours, cooled to room temperature, diluted
with water to about twice its original volume and shaken with
methylene chloride. The organic phase is washed with saturated
aqueous sodium chloride solution, dried with sodium sulphate and
filtered. From the filtrate, the solvent is carefully distilled off
under reduced pressure.
[0254] This gives 2.6 g (92% of theory) of ethyl
(S)-2,4-dichloro-3-[(2-ox- o-pyrrolidin-5-yl)-methoxy]-benzoate
(logP=2.14.sup.a)).
USE EXAMPLES
EXAMPLE A
[0255] Pre-Emergence Test
3 Solvent: 5 parts by weight of acetone Emulsifier: 1 part by
weight of alkylaryl polyglycol ether
[0256] 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.
[0257] Seeds of the test plants are sown in normal soil. After 24
hours, the soil is sprayed with the preparation of active compound
such that the particular amount of active compound desired is
applied per unit area. The concentration of active compound in the
spray liquor is chosen such that the particular amount of active
compound desired is applied in 1000 litres of water per
hectare.
[0258] After three weeks, the degree of damage to the plants is
rated in % damage in comparison to the development of the untreated
control. The figures denote:
[0259] 0%=no effect (like untreated control)
[0260] 100%=total destruction
[0261] In this test, for example, the compounds of Preparation
Examples 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 and 11 show strong activity
against weeds, and most of them are tolerated well by crop plants,
such as, for example, maize.
EXAMPLE B
[0262] Post-Emergence Test
4 Solvent: 5 parts by weight of acetone Emulsifier: 1 part by
weight of alkylaryl polyglycol ether
[0263] 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.
[0264] Test plants with a height of 5-15 cm are sprayed with the
preparation of active compound such that the particular amounts of
active compound desired are applied per unit area. The
concentration of the spray liquor is chosen so that the particular
amounts of active compound desired are applied in 1000 l of
water/ha.
[0265] After three weeks, the degree of damage to the plants is
rated in % damage in comparison to the development of the untreated
control.
[0266] The figures denote:
[0267] 0%=no effect (like untreated control)
[0268] 100%=total destruction
[0269] In this test, for example, the compounds of Preparation
Examples 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 and 13 show strong
activity against weeds, and some are tolerated well by crop plants,
such as for example, maize.
* * * * *