Hetaryl substituted homotetramic and homotetronic acids and their use thereof as pesticides
View Patent ↗The present invention relates to new hetaryl-substituted homotetramic and homotetronic acids of the formula (I) in which A, B, Q 1 , Q 2 , W, G and Het have the meanings stated in the disclosure, to a plurality of processes for their preparation, and to their use as pesticides, microbicides, and herbicides.
1. Compounds of the formula (I)
in which
Het represents
W represents oxygen
X represents hydrogen or C 1 –C 6 -alkyl,
Y represents halogen, C 1 –C 6 -alkyl, C 1 –C 6 -halogenoalkyl, C 1 –C 6 -alkoxy, C 1 –C 6 -halogenoalkoxy, or a group
in which
V 1 represents hydrogen, halogen, C 1 –C 12 -alkyl, C 1 –C 6 -alkoxy,_C 1 –C 6 -alkylthio, C 1 –C 6 -alkylsulphinyl, C 1 –C 6 -alkylsulphonyl, C 1 –C 4 -halogeno-alkyl, C 1 –C 4 -halogenoalkoxy, nitro, cyano, or represents phenyl, phenoxy, phenoxy-C 1 –C 4 -alkyl, phenyl-C 1 –C 4 -alkoxy, phenylthio-C 1 –C 4 -alkyl, or phenyl-C 1 –C 4 -alkylthio, each of which is optionally monosubstituted or polysubstituted by halogen, C 1 –C 6 -alkyl, C 1 –C 6 -alkoxy, C 1 –C 4 -halogenoalkyl, C 1 –C 4 -halogenoalkoxy, nitro, or cyano, and
V 2 and V 3 independently of one another represent hydrogen, halogen, C 1 –C 6 -alkyl, C 1 –C 6 -alkoxy, C 1 –C 4 -halogenoalkyl, or C 1 –C 4 -halogenoalkoxy, or
V 1 and V 2 together with the carbon atoms to which they are bonded represent a 5- or 6-membered cycle that is optionally substituted by C 1 –C 4 -alkyl or halogen and in which one to three carbon atoms is optionally replaced by oxygen, sulphur, or nitrogen,
A represents hydrogen; optionally halogen-substituted alkyl, alkenyl, alkoxyalkyl, polyalkoxyalkyl, or alkylthioalkyl; optionally substituted saturated or unsaturated cycloalkyl in which one or more ring atoms is optionally replaced by a hetero atom; or aryl, arylalkyl or hetaryl, each of which is optionally substituted by halogen, alkyl, halogenoalkyl, alkoxy, halogenoalkoxy, cyano, or nitro,
B represents hydrogen or alkyl, or
A and B together with the carbon atom to which they are bonded represent a saturated or unsaturated, unsubstituted or substituted cycle that optionally contains at least one hetero atom;
Q 1 represents hydrogen; alkyl; alkoxyalkyl; optionally substituted cycloalkyl in which one methylene group is optionally replaced by oxygen or sulphur; or optionally substituted phenyl,
Q 2 represents hydrogen or alkyl, or
Q 1 and Q 2 together with the carbon atom to which they are bonded represent an unsubstituted or substituted cycle that optionally contains one hetero atom, and
G represents hydrogen (a) or one of the groups
in which
L represents oxygen or sulphur,
M represents oxygen or sulphur,
R 1 represents optionally halogen-substituted alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl, or polyalkoxyalkyl; cycloalkyl that is optionally substituted by halogen, alkyl, or alkoxy and that is optionally interrupted by one or more hetero atoms; or optionally substituted phenyl, phenylalkyl, hetaryl, phenoxyalkyl, or hetaryloxyalkyl, and
R 2 represents optionally halogen-substituted alkyl, alkenyl, alkoxyalkyl, or polyalkoxyalkyl; or optionally substituted cycloalkyl, phenyl, or benzyl.
2. A Compound of formula (I) according to claim 1 in which
Het represents
W represents oxygen,
X represents hydrogen or C 1 –C 6 -alkyl,
Y represents halogen, C 1 –C 6 -alkyl, C 1 –C 6 -halogenoalkyl, C 1 –C 6 -alkoxy, C 1 –C 6 -halogenoalkoxy, or a group
in which
V 1 represents hydrogen, halogen, C 1 –C 12 -alkyl, C 1 –C 6 -alkoxy, C 1 –C 6 -alkylthio, C 1 –C 6 -alkylsulphinyl, C 1 –C 6 -alkylsulphonyl, C 1 –C 4 -halogenoalkyl, C 1 –C 4 -halogenoalkoxy, nitro, cyano, or represents phenyl, phenoxy, phenoxy-C 1 –C 4 -alkyl, phenyl-C 1 –C 4 -alkoxy, phenylthio-C 1 –C 4 -alkyl or phenyl-C 1 –C 4 -alkylthio, each of which is optionally monosubstituted or polysubstituted by halogen, C 1 –C 6 -alkyl, C 1 –C 6 -alkoxy, C 1 –C 4 -halogenoalkyl, C 1 –C 4 -halogenoalkoxy, nitro, or cyano, and
V 2 and V 3 independently of one another represent hydrogen, halogen, C 1 –C 6 -alkyl, C 1 –C 6 -alkoxy, C 1 –C 4 -halogenoalkyl, or C 1 –C 4 -halogenoalkoxy, or
V 1 and V 2 together with the carbon atoms to which they are bonded represent a 5- or 6-membered cycle which is optionally substituted by C 1 –C 4 -alkyl or halogen and in which one to three carbon atoms is optionally replaced by oxygen, sulphur or nitrogen,
A represents hydrogen; C 1 –C 12 -alkyl, C 3 –C 8 -alkenyl, or C 1 –C 6 -alkoxy-C 1 –C 4 -alkyl, each of which is optionally substituted by halogen; optionally halogen-, C 1 –C 4 -alkyl-, or C 1 –C 4 -alkoxy-substituted C 3 –C 8 -cycloalkyl, or C 3 –C 6 -cyclo-alkyl-C 1 –C 4 -alkyl in which one or two ring members that are not directly adjacent are optionally replaced by oxygen and/or sulphur; or phenyl, benzyl, hetaryl having 5 to 6 ring atoms, or hetaryl-C 1 –C 4 -alkyl having 5 to 6 ring atoms each of which phenyl, benzyl, hetaryl, or hetaryl-C 1 –C 4 -alkyl group is optionally substituted by halogen, C 1 –C 6 -alkyl, C 1 –C 6 -halogenoalkyl, C 1 –C 6 -alkoxy, C 1 –C 6 -halogenoalkoxy, cyano, or nitro,
B represents hydrogen or C 1 –C 6 -alkyl, or
A, B, and the carbon atom to which they are bonded represent saturated C 3 –C 10 -cycloalkyl or unsaturated C 5 –C 10 -cycloalkyl in which one ring member is optionally replaced by oxygen or sulphur and that are optionally mono-substituted or disubstituted by C 1 –C 6 -alkyl, C 3 –C 8 -cycloalkyl, C 1 –C 6 -halogenoalkyl, C 1 –C 6 -alkoxy, C 1 –C 6 -alkylthio, halogen, or phenyl,
Q 1 represents hydrogen; C 1 –C 6 -alkyl; C 1 –C 6 -alkoxy-C 1 –C 2 -alkyl; C 3 –C 8 -cycloalkyl in which one methylene group is optionally replaced by oxygen or sulphur and that is optionally substituted by fluorine, chlorine, C 1 –C 4 -alkyl, C 1 –C 2 -halogenoalkyl, or C 1 –C 4 -alkoxy; or phenyl that is optionally substituted by halogen, C 1 –C 4 -alkyl, C 1 –C 4 -alkoxy, C 1 –C 2 -halogenoalkyl, C 1 –C 2 -halogeno-alkoxy, cyano, or nitro,
Q 2 represents hydrogen or C 1 –C 4 -alkyl, or
Q 1 and Q 2 together with the carbon atom to which they are bonded represent C 3 –C 7 -cycloalkyl in which one ring member is optionally replaced by oxygen or sulphur and that is optionally substituted by C 1 –C 6 -alkyl, C 1 –C 6 -alkoxy, or C 1 –C 2 -halogenoalkyl, and
G represents hydrogen (a) or one of the groups
in which
L represents oxygen or sulphur,
M represents oxygen or sulphur,
R 1 represents C 1 –C 20 -alkyl, C 1 –C 20 -alkenyl, C 1 –C 8 -alkoxy-C 1 –C 8 -alkyl, C 1 –C 8 -alkylthio-C 1 –C 8 -alkyl, or poly-C 1 –C 8 -alkoxy-C 1 –C 8 -alkyl, each of which is optionally substituted by halogen; C 3 –C 8 -cycloalkyl in which one or more ring members that are not directly adjacent are optionally replaced by oxygen and/or sulphur and that is optionally substituted by halogen, C 1 –C 6 -alkyl, or C 1 –C 6 -alkoxy; phenyl that is optionally substituted by halogen, cyano, nitro, C 1 –C 6 -alkyl, C 1 –C 6 -alkoxy, C 1 –C 6 -halogenoalkyl, C 1 –C 6 -halogenoalkoxy, C 1 –C 6 -alkylthio, or C 1 –C 6 -alkylsulphonyl; phenyl-C 1 –C 6 -alkyl that is optionally substituted by halogen, nitro, cyano, C 1 C 6 -alkyl, C 1 –C 6 -alkoxy, C 1 –C 6 -halogeno-alkyl, or C 1 –C 6 -halogenoalkoxy; 5- or 6-membered hetaryl that is optionally substituted by halogen, C 1 –C 6 -alkyl, or trifluoromethyl; phenoxy-C 1 –C 6 -alkyl that is optionally substituted by halogen or C 1 –C 6 -alkyl; or 5- or 6-membered hetaryloxy-C 1 –C 6 -alkyl that is optionally substituted by halogen, amino, or C 1 –C 6 -alkyl, and
R 2 represents C 1 –C 20 -alkyl, C 2 –C 20 -alkenyl, C 1 –C 8 -alkoxy-C 2 –C 8 -alkyl, or poly-C 1 –C 8 -alkoxy-C 2 –C 8 -alkyl, each of which is optionally substituted by halogen; C 3 –C 8 -cycloalkyl that is optionally substituted by halogen, C 1 –C 6 -alkyl, or C 1 –C 6 -alkoxy; or phenyl or benzyl, each of which is optionally substituted by halogen, cyano, nitro, C 1 –C 6 -alkyl, C 1 –C 6 -alkoxy, C 1 –C 6 -halogenoalkyl, or C 1 –C 6 -halogenalkoxy.
3. A compound of formula (I) according to claim 1 in which
Het represents
W represents oxygen,
X represents hydrogen or C 1 –C 4 -alkyl;
Y represents chlorine, bromine, C 1 –C 4 -alkyl, C 1 –C 4 -halogenoalkyl, C 1 –C 4 -alkoxy, C 1 –C 4 -halogenoalkoxy, or a group
in which
V 1 represents hydrogen, fluorine, chlorine, bromine, C 1 –C 6 -alkyl, C 1 –C 4 -alkoxy, C 1 –C 2 -halogenoalkyl, C 1 –C 2 -halogenalkoxy, nitro, or cyano; or phenyl, phenoxy, phenoxy- 1 –C 2 -alkyl, phenyl-C 1 –C 2 -alkoxy, phenyl-thio-C 1 –C 2 -alkyl, or phenyl-C 1 –C 2 -alkylthio, each of which is optionally monosubstituted or disubstituted by fluorine, chlorine, bromine, C 1 –C 4 -alkyl, C 1 –C 4 -alkoxy, C 1 –C 2 -halogenoalkyl, C 1 –C 2 -halogenoalkoxy, nitro, or cyano, and
V 2 represents hydrogen, fluorine, chlorine, bromine, C 1 –C 4 -alkyl, C 1 –C 4 -alkoxy, C 1 –C 2 -halogenoalkyl, or C 1 –C 2 -halogenoalkoxy, or
V 1 and V 2 together with the carbon atoms to which they are bonded represent a 5- or 6-membered cycle in which one or two carbon atoms is optionally replaced by oxygen and that is optionally substituted by fluorine or methyl,
A represents hydrogen; C 1 –C 8 -alkyl or C 1 –C 4 -alkoxy- 1 –C 2 -alkyl, each of which is optionally substituted by fluorine; C 5 –C 6 -cycloalkyl or C 3 –C 6 -cycloalkyl-C 1 –C 2 -alkyl in which one ring member is optionally replaced by oxygen or sulphur and that is optionally substituted by fluorine, chlorine, methyl, ethyl, or methoxy; or phenyl or benzyl, each of which is optionally substituted by fluorine, chlorine, bromine, C 1 –C 4 -alkyl, C 1 –C 2 -halogenoalkyl, C 1 –C 4 -alkoxy, or C 1 –C 2 -halogenoalkoxy,
B represents hydrogen or C 1 –C 4 -alkyl, or
A, B, and the carbon atom to which they are bonded represent saturated C 5 –C 7 -cycloalkyl in which one ring member is optionally replaced by oxygen and that is optionally monosubstituted by C 1 –C 4 -alkyl, trifluoromethyl, or C 1 –C 4 -alkoxy,
Q 1 represents hydrogen, C 1 –C 4 -alkyl, or C 1 –C 4 -alkoxy-C 1 –C 2 -alkyl; or C 3 –C 6 -cycloalkyl in which one methylene group is optionally replaced by oxygen and that is optionally substituted by methyl or methoxy,
Q 2 represents hydrogen, methyl, or ethyl, or
Q 1 and Q 2 together with the carbon atom to which they are bonded represent saturated C 5 –C 6 -cycloalkyl in which one ring member is optionally replaced by oxygen and that is optionally substituted by C 1 –C 4 -alkyl or C 1 –C 4 -alkoxy, and
G represents hydrogen (a) or one of the groups
in which
L represents oxygen or sulphur,
M represents oxygen or sulphur,
R 1 represents C 1 –C 16 -alkyl, C 2 –C 16 -alkenyl, C 1 –C 4 -alkoxy-C 1 –C 2 -alkyl, or C 1 –C 4 -alkylthio-C 1 –C 2 -alkyl, each of which is optionally substituted by fluorine or chlorine; C 3 –C 7 -cycloalkyl in which one or two ring members that are not directly adjacent are optionally replaced by oxygen and/or sulphur and that is optionally substituted by fluorine, chlorine, C 1 –C 5 -alkyl or C 1 –C 5 -alkoxy; phenyl that is optionally substituted by fluorine, chlorine, bromine, cyano, nitro, C 1 –C 4 -alkyl, C 1 –C 4 -alkoxy, trifluoromethyl, or trifluoromethoxy; or pyridyl or thienyl, each of which is optionally substituted by fluorine, chlorine, bromine, methyl, ethyl, or trifluoromethyl, and
R 2 represents C 1 –C 16 -alkyl, C 2 –C 16 -alkenyl, or C 1 –C 4 -alkoxy-C 2 –C 4 -alkyl, each of which is optionally substituted by fluorine; C 3 –C 7 -cyclo-alkyl that is optionally substituted by methyl, ethyl or methoxy; or phenyl or benzyl, each of which is optionally substituted by fluorine, chlorine, bromine, cyano, nitro, C 1 –C 4 -alkyl, C 1 –C 3 -alkoxy, trifluoro-methyl, or trifluoromethoxy.
4. A compound of formula (I) according to claim 1 in which
Het represents
W represents oxygen,
X represents methyl, ethyl, n-propyl, isopropyl, n-butyl, or isobutyl,
Y represents methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, or the group
in which
V 1 represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, trifluoromethyl, or trifluoromethoxy, and
V 2 represents hydrogen, fluorine, chlorine, methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, trifluoromethyl, or trifluoromethoxy,
A represents hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, methoxymethyl, or ethoxymethyl,
B represents hydrogen, methyl, or ethyl, or
A, B, and the carbon atom to which they are bonded represent saturated C 5 –C 6 -cycloalkyl in which one ring member is optionally replaced by oxygen and that is optionally monosubstituted by methyl, ethyl, n-propyl, isopropyl, butyl, trifluoromethyl, methoxy, ethoxy, n-propoxy, or n-butoxy,
Q 1 represents hydrogen, methyl, ethyl, propyl, isopropyl, cyclopropyl, cyclopentyl, or cyclohexyl,
Q 2 represents hydrogen, methyl, or ethyl, or
Q 1 and Q 2 jointly with the carbon to which they are bonded represent saturated C 5 –C 6 -cycloalkyl in which one ring member is optionally replaced by oxygen and that is optionally substituted by methyl, ethyl, propyl, isopropyl, methoxy, ethoxy, propoxy, or butoxy,
G represents hydrogen (a) or one of the groups
in which
L represents oxygen or sulphur,
M represents oxygen or sulphur,
R 1 represents C 1 –C 1 -alkyl, C 2 –C 14 -alkenyl, C 1 –C 4 -alkoxy-C 1 –C 2 -alkyl, or C 1 –C 4 -alkylthio-C 1 –C 2 -alkyl, each of which is optionally substituted by fluorine or chlorine; C 3 –C 6 -cycloalkyl in which one or two ring members that are not directly adjacent are optionally replaced by oxygen and/or sulphur and that is optionally substituted by fluorine, chlorine, methyl, ethyl, or methoxy; phenyl that is optionally substituted by fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, isopropyl, tert-butyl, methoxy, trifluoromethyl, or trifluoromethoxy; or thienyl or pyridyl, each of which is optionally substituted by fluorine, chlorine, bromine, or methyl, and
R 2 represents C 1 –C 14 -alkyl, C 2 –C 14 -alkenyl, or C 2 –C 4 -alkoxy-C 2 –C 3 -alkyl, each of which is optionally substituted by fluorine; C 3 –C 6 -cycloalkyl that is optionally substituted by methyl, ethyl, or methoxy; or phenyl or benzyl, each of which is optionally substituted by fluorine, chlorine, cyano, nitro, methyl, ethyl, isopropyl, tert-butyl, methoxy, trifluoromethyl, or trifluoromethoxy.
5. A compound of formula (I) according to claim 1 in which
Het represents
W represents oxygen,
X represents methyl, ethyl, n-propyl, or i-propyl,
Y represents
A represents hydrogen or methyl,
B represents hydrogen or methyl, or
A, B, and the carbon atom to which they are bonded represent saturated C 6 -cycloalkyl in which one ring member is optionally replaced by oxygen,
Q 1 represents hydrogen or methyl,
Q 2 represents hydrogen or methyl, or
Q 1 and Q 2 jointly with the carbon to which they are bonded represent saturated C 6 -cycloalkyl in which one ring member is optionally replaced by oxygen,
G represents hydrogen (a) or one of the groups
in which
M represents oxygen or sulphur,
R 1 represents C 1 –C 4 -alkyl, or C 1 –C 4 -alkoxy-C 1 –C 2 -alkyl; or phenyl or pyridyl, each of which is optionally substituted by chlorine, and
R 2 represents C 1 –C 4 -alkyl, phenyl, or benzyl.
6. A process for the preparation of a compound of formula (I) according to claim 1 comprising
(A) for substituted 5,6-dihydropyrones of formula (I-2-a)
in which A, B, Q 1 , Q 2 , and Het have the meanings given for formula (I), subjecting to an intramolecular condensation reaction an O-acyl hydroxycarboxylic ester of formula (III)
in which
A, B, Q 1 , Q 2 , and Het have the meanings given for formula (I), and
R 8 represents alkyl,
in the presence of a diluent and in the presence of a base,
(B) for compounds of formula (I-2-b)
in which A, B, Q 1 , Q 2 , R 1 , and Het have the meanings given for formula (I), reacting a compound of the formulas (I-2-a) with
(α) an acid halide of formula (IV)
in which
R 1 has the meanings given for formula (I), and
Hal represents halogen, or
(β) a carboxylic anhydride of the formula (V)
R 1 —CO—O—CO—R 1 (V)
in which R 1 has the meanings given for formula (I), optionally in the presence of a diluent and optionally in the presence of an acid binder;
(C) for-compounds of formula (I-2-c)
in which
A, B, Q 1 , Q 2 , R 2 , M, and Het have the meanings given for formula (I), and
L represents oxygen, reacting a compound of the formulas (I-2-a) with a chloroformic ester or a chloroformic thioester of formula (VI)
R 2 -M-CO—Cl (VI)
in which R 2 and M have the meanings given for formula (I), optionally in the presence of a diluent and optionally in the presence of an acid binder; or
(D) for compounds of formulas (I-2-c)
in which
A, B, Q 1 , Q 2 , R 2 , M, and Het have the meanings given for formula (I), and
L represents sulphur, reacting a compound of the formulas (I-2-a) with a chloromonothioformic ester or a chlorodithioformic ester of formula (VII)
in which R 2 and M have the meanings given for formula (I), optionally in the presence of a diluent and optionally in the presence of an acid binder.
7. A pesticide, microbicide, or herbicide comprising an effective amount of a compound of formula (I) according to claim 1 and one or more extenders and/or surfactants.
8. A method of controlling animal pests comprising allowing an effective amount of a compound of formula (I) according to claim 1 to act on the pests and/or their environment.
9. A method of controlling undesired vegetation comprising allowing an effective amount of a compound of formula (I) according to claim 1 to act on the undesired vegetation and/or its environment.
10. A method of controlling fungi comprising allowing an effective amount of a compound of formula (I) according to claim 1 to act on the fungi and/or their environment.
11. A process for the preparation of a pesticide, microbicide, or herbicide comprising mixing a compound of formula (I) according to claim 1 with one or more extenders and/or surfactants.