1,4 diaryl-2,3-difluoro-2-butene insecticidal and acaricidal...

Drug – bio-affecting and body treating compositions – Designated organic active ingredient containing – Ether doai

Reexamination Certificate

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C514S277000, C514S744000, C570S129000, C568S635000

Reexamination Certificate

active

06506800

ABSTRACT:

DESCRIPTION
The present invention provides 1,4-diaryl-2,3-difluoro-2-butene compounds which are useful as insecticidal and acaricidal agents. The compounds are also useful for protecting plants from damage caused by insect and acarid attack and infestation.
1,4-diaryl-2,3-difluoro-2-butenes of the present invention have the structural formula I
wherein
Ar is
phenyl which is unsubstituted or substituted with any combination of from one to three halogen, C
1
-C
4
alkyl, C
1
-C
4
-haloalkyl, C
1
-C
4
-alkoxy, C
1
-C
4
-haloalkoxy or hydroxy groups,
1- or 2-naphthyl which is unsubstituted or substituted with any combination of from one to three halogen, C
1
-C
4
-alkyl, C
1
-C
4
-haloalkyl, C
1
-C
4
-alkoxy or C
1
-C
4
-haloalkoxy groups, or
a 5- or 6-membered heteroaromatic ring containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur atom or oxygen atom or one or two sulfur and/or oxygen atoms which is unsubstituted or substituted with any combination of from one to three halogen, C
1
-C
4
-alkyl, C
1
-C
4
haloalkyl, C
1
-C
4
-alkoxy or C
1
-C
4
-haloalkoxy groups;
R is C
2
-C
6
-alkenyl, C
4
-C
6
-cycloalkenyl or C
1
-C
2
-alkoxy-C
2
-C
6
-alkyl;
Ar
1
is
phenoxyphenyl which is unsubstituted or substituted with any combination of from one to six halogen, C
1
-C
4
-alkyl, C
1
-C
4
-haloalkyl, C
1
-C
4
-alkoxy or C
1
-C
4
-haloalkoxy groups,
phenyl which is unsubstituted or substituted with any combination of from one to five halogen, C
1
-C
4
-alkyl, C
1
-C
4
-haloalkyl, C
1
-C
4
-alkoxy or C
1
-C
4
-haloalkoxy groups,
biphenyl which is unsubstituted or substituted with any combination of from one to five halogen, C
1
-C
4
-alkyl, C
1
-C
4
-haloalkyl, C
1
-C
4
-alkoxy or C
1
-C
4
-haloalkoxy groups,
phenoxypyridyl which is unsubstituted or substituted with any combination of from one to five halogen, C
1
-C
4
-alkyl, C
1
-C
4
-haloalkyl C
1
-C
4
-alkoxy or C
1
-C
4
-haloalkoxy groups,
benzylpyridyl which is unsubstituted or substituted with any combination of from one to five halogen, C
1
-C
4
-alkyl, C
1
-C
4
-haloalkyl, C
1
-C
4
-alkoxy or C
1
-C
4
-haloalkoxy groups,
benzylphenyl which is unsubstituted or substituted with any combination of from one to five halogen, C
1
-C
4
-alkyl, is C
1
-C
4
-haloalkyl, C
1
-C
4
-alkoxy or C
1
-C
4
-haloalkoxy groups,
benzoylphenyl which is unsubstituted or substituted with any combination of from one to five halogen, C
1
-C
4
-alkyl, C
1
-C
4
-haloalkyl, C
1
-C
4
-alkoxy or C
1
-C
4
-haloalkoxy groups,
1- or 2-naphthyl which is unsubstituted or substituted with any combination of from one to three halogen, C
1
-C
4
-alkyl, C
1
-C
4
-haloalkyl, C
1
-C
4
-alkoxy or C
1
-C
4
-haloalkoxy groups, or
a 5- or 6-membered heteroaromatic ring containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur atom or oxygen atom or one or two sulfur and/or oxygen atoms which is unsubstituted or substituted with any combination of from one to three halogen, C
1
-C
4
-alkyl, C
1
-C
4
-haloalkyl, C
1
-C
4
-alkoxy or C
1
-C
4
-haloalkoxy groups, and
the optical isomers thereof, and
the (E)- and (Z)-isomers thereof.
This invention also provides intermediates and methods for the preparation of compounds of formula I, compositions containing the compounds, and methods for using the compounds and compositions.
U.S. Pat. No. 5,248,834 generically discloses certain 1-aryl-1-(3-aryl-1,2-difluoroprop-1-enyl)cyclopropane compounds.
EP-A 916 640 describes certain insecticidal and acaricidal 1,4-diaryl-2,3-difluoro-2-butenes, as well as methods for their preparation. Said application, however, does not disclose 1,4-diaryl-2,3-difluoro-2-butenes having alkoxy alkyl or alkenyl substituents in the 1-position.
The insecticidal and acaricidal activity of the compounds disclosed in the above-mentioned prior art in many cases is not fully satisfying.
It was, therefore, an object of the present invention to provide compounds which are more effective for the control of insect and acarid pests.
Accordingly, the 1,4-diaryl-2,3-difluoro-2-butene compounds of formula I have been found. Furthermore, intermediates and methods for the preparation of compounds of formula I as well as compositions containing them have been found.
The present invention also provides a method for the control of insect or acarid pests which comprises contacting said pests or their food supply, habitat or breeding grounds with a pesticidally effective amount of a compound of formula I.
The present invention also provides a method for the protection of growing plants from attack or infestation by insect or acarid pests which comprises applying to the foliage of the plants, or to the soil or water in which they are growing, a pesticidally effective amount of a compound of formula I.
In formula I above, 5- and 6-membered heteroaromatic rings containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur atom or oxygen atom or one or two sulfur and/or oxygen atoms include, but are not limited to, pyridyl, pyrazolyl, imidazolyl, triazolyl, isoxazolyl, tetrazolyl, pyrazinyl, pyridazinyl, triazinyl, furanyl, thienyl and thiazolyl rings each unsubstituted or substituted as described in formula I above.
Exemplary of halogen hereinabove are fluorine, chlorine, bromine and iodine;
The term “alkyl” is defined as a saturated, straight or branched chain hydrocarbon with 1 to 4 or 2 to 6 carbon atoms, such as methyl, ethyl, propyl, 1-methyl-ethyl, butyl, 1-methyl-propyl, 2-methyl-propyl, 1,1-dimethyl-propyl, pentyl, 1-methyl-butyl, 2-methyl-butyl, 3-methyl-butyl, 2,2-dimethyl-propyl, 1-ethyl-propyl, hexyl, 1,1-dimethyl-propyl, 1,2-dimethyl-propyl, 1-methyl-pentyl, 2-methyl-pentyl, 3-methyl-pentyl, 4-methyl-pentyl, 1,1-dimethyl-butyl, 1,2-dimethyl-butyl, 1,3-dimethyl-butyl, 2,2-dimethyl-butyl, 2,3-dimethyl-butyl, 3,3-dimethyl-butyl, 1-ethyl-butyl, 2-ethyl-butyl, 1,1,2-trimethyl-propyl, 1,2,2-tri-methyl-propyl, 1-ethyl-1-methyl-propyl und 1-ethyl-2-methyl-propyl;
The term “alkoxy” is defined as a saturated, straight or branched chain hydrocarbon with 1 to 2 or 4 carbon atoms (as described above) which is bond to the backbone via an oxygen (—O—) atom;
The term “cycloalkyl” is defined as a monocyclic, saturated hydrocarbon group with 3 to 6 carbon ring atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl;
The term “haloalkyl” is defined as an alkyl group, as defined above, wherein the hydrogen atoms may be partially or totally substituted with halogen atoms as defined above, wherein the halogen atoms may be the same or different, for example C
1
-C
2
-haloalkyl such as chloro-methyl, bromomethyl, dichloro-methyl, trichloro-methyl, fluoro-methyl, difluoro-methyl, trifluoro-methyl, chloro-fluoro-methyl, dichlorofluoro-methyl, chloro-difluoro-methyl, 1-chloro-ethyl, 1-bromo-ethyl, 1-fluoro-ethyl, 2-fluoro-ethyl, 2,2-difluoro-ethyl, 2,2,2-trifluoro-ethyl, 2-chloro-2-fluoro-ethyl, 2-chloro-2,2-difluoro-ethyl, 2,2-dichloro-2-fluoro-ethyl, 2,2,2-trichloro-ethyl and pentafluoro-ethyl;
The term “haloalkoxy” is defined as an alkoxy group as defined above, wherein the hydrogen atoms may be partially or totally substituted with one or more halogen atoms as defined above, wherein the halogen atoms may be the same or different;
The term halocycloalkyl is defined as a cycloalkyl group as defined above, wherein the hydrogen atoms may be partially or totally substituted with one or more halogen atoms as defined above, wherein the halogen atoms may be the same or different;
The term “alkenyl” is defined as an unsaturated, straight or branched chain hydrocarbon with 2 to 6 carbon atoms and a double bond in an arbitrary position, such as ethenyl, 1-propenyl, 2-propenyl, 1-methyl-ethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimet

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