2-phenyl-2-substituted-1,3-diketones
View Patent ↗The invention relates to novel phenyl-substituted cyclopentane- and cyclohexane-1,3-dione derivatives of the formula (I) in which W, X, Y, Z, A, B, Q 1 , Q 2 , Q 3 , Q 4 , G and m are as defined in the disclosure, to processes and intermediates for their preparation and to their use as pesticides, microbicides and/or herbicides.
1. A compound of formula (I)
in which
W represents cyano, halogen, alkyl, alkenyl, alkynyl, alkoxy, haloalkyl, or haloalkoxy,
X represents hydrogen, halogen, alkyl, alkoxy, haloalkyl, haloalkoxy, or cyano,
Y represents hydrogen, halogen, alkyl, alkoxy, haloalkyl, haloalkoxy, cyano, or optionally substituted phenyl,
Z represents hydrogen, halogen, alkyl, alkoxy, haloalkyl, haloalkoxy, or cyano,
G represents halogen or nitro,
m represents the number 0 or 1,
A represents hydrogen; optionally halogen-substituted alkyl, alkenyl, alkoxyalkyl, polyalkoxyalkyl, or alkylthioalkyl; saturated or unsaturated, optionally substituted cycloalkyl in which one or more ring atoms is optionally replaced by a heteroatom; or optionally halogen-, alkyl-, haloalkyl-, alkoxy-, halo-alkoxy-, cyano-, or nitro-substituted aryl, arylalkyl, or hetaryl,
B represents hydrogen or alkyl, or
A and B together with the carbon atom to which they are attached represent a saturated or unsaturated, unsubstituted or substituted cycle that optionally contains one or more heteroatoms, or
A and Q 1 together represent optionally substituted alkanediyl in which two carbon atoms that are not directly adjacent optionally form a further optionally substituted cycle, or
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, hetaryl, phenylalkyl, or hetarylalkyl, and
Q 2 , Q 3 , Q 4 independently of one another represent hydrogen or alkyl, or
Q 1 and Q 2 together with the carbon atom to which they are attached represent a saturated or unsaturated, unsubstituted or substituted cycle that optionally contains a heteroatom.
2. A compound of formula (I) according to claim 1 in which
W represents halogen, C 1 –C 6 -alkyl, C 2 –C 6 -alkenyl, C 2 –C 6 -alkynyl, C 1 –C 6 -alkoxy, C 1 –C 4 -haloalkyl, C 1 –C 4 -haloalkoxy, or cyano,
X represents hydrogen, halogen, C 1 –C 6 -alkyl, C 1 –C 6 -alkoxy, C 1 –C 4 -haloalkyl, C 1 –C 4 -haloalkoxy or cyano,
Y represents hydrogen, halogen, C 1 –C 6 -alkyl, C 1 –C 6 -alkoxy, C 1 –C 4 -haloalkyl, C 1 –C 4 -haloalkoxy, or cyano; or represents the group
in which
V 1 represents hydrogen, halogen, C 1 –C 12 -alkyl, C 1 –C 6 -alkoxy, C 1 –C 6 -alkythio, C 1 –C 6 -alkylsulphinyl, C 1 –C 6 -alkylsulphonyl, C 1 –C 4 -haloalkyl, C 1 –C 4 -haloalkoxy, nitro, or 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 mono- or poly-substituted by halogen, C 1 –C 6 -alkyl, C 1 –C 6 -alkoxy, C 1 –C 4 -haloalkyl, C 1 –C 4 -haloalkoxy, 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 -haloalkyl, or C 1 –C 4 -haloalkoxy, or
V 1 and V 2 together and together with the carbon atoms to which they are attached represent an optionally C 1 –C 4 -alkyl- or halogen-substituted 5- or 6-membered cycle in which one or two carbon atoms are optionally replaced by oxygen, sulphur, or nitrogen,
Z represents hydrogen, halogen, C 1 –C 6 -alkyl, C 1 –C 6 -alkoxy, C 1 –C 4 -haloalkyl, C 1 –C 4 -haloalkoxy, or cyano,
G represents halogen or nitro,
m represents the number 0 or 1,
A represents hydrogen; optionally halogen-substituted C 1 –C 12 -alkyl, C 3 –C 8 -alkenyl, or C 1 –C 6 -alkoxy-C 1 –C 4 -alkyl; optionally halogen-, C 1 –C 4 -alkyl- or C 1 –C 4 -alkoxy-substituted C 3 –C 8 -cycloalkyl or C 3 –C 6 -cycloalkyl-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 optionally halogen-, C 1 –C 6 -alkyl-, C 1 –C 6 -haloalkyl-, C 1 –C 6 -alkoxy-, C 1 –C 6 -haloalkoxy-, cyano-, or nitro-substituted phenyl, benzyl, hetaryl having 5 or 6 ring atoms, or hetaryl-C 1 –C 4 -alkyl having 5 or 6 ring atoms,
B represents hydrogen or C 1 –C 6 -alkyl, or
A, B, and the carbon atom to which they are attached 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 is optionally mono- or disubstituted by C 1 –C 6 -alkyl, C 3 –C 8 -cycloalkyl, C 1 –C 6 -haloalkyl, C 1 –C 6 -alkoxy, C 1 –C 6 -alkylthio, halogen, or phenyl, or
A and Q 1 together represent C 3 –C 6 -alkanediyl which is optionally mono- or disubstituted by identical or different substituents from the group consisting of C 1 –C 4 -alkyl and C 1 –C 4 -alkoxy, or
Q 1 represents hydrogen, C 1 –C 6 -alkyl, or C 1 –C 6 -alkoxy-C 1 –C 2 -alkyl; optionally fluorine-, chlorine-, C 1 –C 4 -alkyl-, C 1 –C 2 -haloalkyl-, or C 1 –C 4 -alkoxy-substituted C 3 –C 8 -cycloalkyl in which one methylene group is optionally replaced by oxygen or sulphur; or optionally halogen-, C 1 –C 4 -alkyl-, C 1 –C 4 -alkoxy, C 1 –C 2 -haloalkyl-, C 1 –C 2 -haloalkoxy-, cyano-, or nitro-substituted phenyl, pyridyl, thienyl, thiazolyl, phenyl-C 1 –C 4 -alkyl, pyridyl-C 1 –C 2 -alkyl, or thiazolyl-C 1 –C 2 -alkyl, and
Q 2 , Q 3 , Q 4 independently of one another represent hydrogen or C 1 –C 4 -alkyl, or
Q 1 and Q 2 together with the carbon atom to which they are attached represent optionally C 1 –C 6 -alkyl-, C 1 –C 6 -alkoxy-, or C 1 –C 2 -haloalkyl-substituted C 3 –C 7 -cycloalkyl in which one ring member is optionally replaced by oxygen or sulphur.
3. A compound of formula (I) according to claim 1 in which
W represents fluorine, chlorine, bromine, C 1 –C 4 -alkyl, C 1 –C 4 -alkoxy, C 1 –C 2 -haloalkyl, C 1 –C 2 -haloalkoxy, or cyano,
X represents hydrogen, fluorine, chlorine, bromine, C 1 –C 4 -alkyl, or C 1 –C 4 -alkoxy,
Y represents hydrogen, fluorine, chlorine, bromine, C 1 –C 6 -alkyl, C 1 –C 6 -alkoxy, C 1 –C 2 -haloalkyl, C 1 –C 2 -haloalkoxy, or cyano; or represents the group
in which
V 1 represents hydrogen, fluorine, chlorine, bromine, C 1 –C 6 -alkyl, C 1 –C 4 -alkoxy, C 1 –C 2 -haloalkyl, C 1 –C 2 -haloalkoxy, nitro, or cyano; or represents phenyl or phenoxy, each of which is optionally mono- or disubstituted by fluorine, chlorine, bromine, C 1 –C 4 -alkyl, C 1 –C 4 -alkoxy, C 1 –C 2 -haloalkyl, C 1 –C 2 -haloalkoxy, nitro, or cyano, and
V 2 represents hydrogen, fluorine, chlorine, C 1 –C 4 -alkyl, C 1 –C 4 -alkoxy, C 1 –C 2 -haloalkyl, or C 1 –C 2 -haloalkoxy, or
V 1 and V 2 together and together with the carbon atoms to which they are attached represent an optionally fluorine- or methyl-substituted 5- or 6-membered cycle in which one or two carbon atoms is optionally replaced by oxygen,
Z represents hydrogen, fluorine, chlorine, bromine, C 1 –C 4 -alkyl, C 1 –C 4 -alkoxy, C 1 –C 2 -haloalkyl, C 1 –C 2 -haloalkoxy, or cyano,
G represents chlorine, bromine, or nitro,
m represents the number 0 or 1,
A represents hydrogen; optionally fluorine-substituted C 1 –C 8 -alkyl or C 1 –C 4 -alkoxy-C 1 –C 2 -alkyl; optionally fluorine-, chlorine-, methyl-, ethyl-, or methoxy-substituted 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; or optionally fluorine-, chlorine-, bromine-, C 1 –C 4 -alkyl-, C 1 –C 2 -haloalkyl-, C 1 –C 4 -alkoxy-, or C 1 –C 2 -haloalkoxy-substituted phenyl or benzyl,
B represents hydrogen or C 1 –C 4 -alkyl, or
A, B, and the carbon atom to which they are attached 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, with the proviso that in this case Q 1 represents only hydrogen, or
A and Q 1 together represent C 3 –C 4 -alkanediyl that is optionally mono- or disubstituted by methyl, ethyl, methoxy, or ethoxy, or
Q 1 represents hydrogen, C 1 –C 6 -alkyl, or C 1 –C 4 -alkoxy-C 1 –C 2 -alkyl; optionally methyl- or methoxy-substituted C 3 –C 6 -cycloalkyl in which one methylene group is optionally replaced by oxygen; or optionally fluorine-, chlorine-, bromine-, C 1 –C 4 -alkyl-, C 1 –C 4 -alkoxy-, trifluoromethyl-, or trifluoromethoxy-substituted phenyl or benzyl, and
Q 2 , Q 3 , Q 4 independently of one another represent hydrogen, methyl, or ethyl, or
Q 1 and Q 2 together with the carbon to which they are attached represent optionally C 1 –C 4 -alkyl- or C 1 –C 4 -alkoxy-substituted saturated C 5 –C 6 -cycloalkyl in which one ring member is optionally replaced by oxygen, with the proviso that in this case A represents only hydrogen.
4. A compound of formula (I) according to claim 1 in which
W represents chlorine, bromine, methyl, ethyl, propyl, methoxy, ethoxy, trifluoromethyl, difluoromethoxy, trifluoromethoxy, or cyano,
X represents hydrogen, chlorine, bromine, methyl, ethyl, propyl, methoxy, or ethoxy,
Y represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl, n-propyl, i-butyl, CH(CH 3 )-i-butyl, methoxy, ethoxy, trifluoromethyl, trifluoromethoxy, difluoromethoxy, or cyano; or represents 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, or trifluoromethyl,
Z represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl, propyl, methoxy, ethoxy, trifluoromethyl, trifluoromethoxy, difluoromethoxy, or cyano,
G represents chlorine, bromine, or nitro,
m represents the number 0 or 1,
A represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, methoxymethyl, or ethoxymethyl,
B represents hydrogen, methyl, or ethyl, or
A, B, and the carbon atom to which they are attached represent saturated C 5 –C 7 -cycloalkyl in which one ring member is optionally replaced by oxygen and that is optionally monosubstituted by methyl, ethyl, isopropyl, trifluoromethyl, methoxy, ethoxy, n-propoxy, n-butoxy, or isobutoxy, with the proviso that in this case Q 1 , Q 2 , Q 3 , and Q 4 represent only hydrogen, or
A and Q 1 together represent C 3 –C 4 -alkanediyl, or
Q 1 represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-hexyl, cyclopropyl, cyclopentyl, or cyclohexyl, and
Q 2 , Q 3 , Q 4 independently of one another represent hydrogen, methyl, or ethyl, or
Q 1 and Q 2 together with the carbon to which they are attached represent optionally methyl-, ethyl-, methoxy-, ethoxy-, n-propoxy-, or n-butoxy-substituted saturated C 5 –C 6 -cycloalkyl in which one ring member is optionally replaced by oxygen, with the proviso that in this case A, B, Q 3 , and Q 4 represent only hydrogen.
5. A compound of formula (I) according to claim 1 in which
W represents methyl or chlorine,
Y represents phenyl that is optionally mono- or disubstituted by fluorine or chlorine; or represents chlorine, bromine, methyl, ethyl, n-propyl, i-butyl, CH(CH 3 )-i-butyl, or trifluoromethyl,
Z represents hydrogen,
G represents chlorine,
m represents 0 or 1,
A represents hydrogen or methyl,
B represents hydrogen or methyl, or
A, B, and the carbon atom to which they are attached represent C 5 –C 7 -cycloalkyl, with the proviso that in this case Q 1 and Q 2 represent only hydrogen,
Q 1 represents hydrogen, methyl, ethyl, i-propyl, or n-hexyl,
Q 2 represents hydrogen or methyl, or
Q 1 , Q 2 , and the carbon atom to which they are attached represent C 5 –C 6 -cycloalkyl, with the proviso that in this case A and B represent only hydrogen,
Q 3 represents hydrogen, and
Q 4 represents hydrogen.
6. A process for preparing compounds of formula (I) according to claim 1 comprising
(A) for compounds of formulas (I-1) or (I-2)
in which
A, B, Q 1 , Q 2 , Q 3 , Q 4 , W, X, Y, and Z are as defined for formula (I) of claim 1 , and
G represents halogen,
reacting a compound of formulas (II-1) or (II-2)
in which A, B, Q 1 , Q 2 , Q 3 , Q 4 , W, X, Y, and Z are as defined for formula (I) of claim 1 ,
with a halogenating agent in the presence of a solvent and optionally in the presence of a free-radical initiator, and
(B) for compounds of formulas (I-1) or (I-2)
in which
A, B, Q 1 , Q 2 , Q 3 , Q 4 , W, X, Y, and Z are as defined for formula (I) of claim 1 , and
G represents nitro,
reacting a compound of formulas (II-1) or (II-2)
in which A, B, Q 1 , Q 2 , Q 3 , Q 4 , W, X, Y, and Z are as defined for formula (I) of claim 1 ,
with a nitrating agent in the presence of a solvent.
7. A process according to claim 6 in which the nitrating agent is fuming nitric acid.
8. A composition for controlling pests, unwanted vegetation, and/or unwanted microorganisms comprising one or more compounds of formula (I) according to claim 1 and one or more extenders and/or surfactants.
9. A method for controlling animal pests comprising allowing an effective amount of one or more compounds of formula (I) according to claim 1 to act on the pests and/or their habitat.
10. A method for controlling unwanted vegetation comprising allowing an effective amount of one or more compounds of formula (I) according to claim 1 to act on the unwanted vegetation and/or its habitat.
11. A method for controlling unwanted microorganisms comprising allowing an effective amount of one or more compounds of formula (I) according to claim 1 to act on the unwanted microorganisms and/or their habitat.
12. A process for preparing a composition for controlling pests, unwanted vegetation, and/or unwanted microorganisms comprising mixing one or more compounds of formula (I) according to claim 1 with one or more extenders and/or surfactants.