Drug – bio-affecting and body treating compositions – Designated organic active ingredient containing – Having -c- – wherein x is chalcogen – bonded directly to...
Reexamination Certificate
2002-01-11
2003-07-15
Ramsuer, Robert W. (Department: 1626)
Drug, bio-affecting and body treating compositions
Designated organic active ingredient containing
Having -c-, wherein x is chalcogen, bonded directly to...
C548S365700
Reexamination Certificate
active
06593358
ABSTRACT:
The present invention relates to thienyl-pyrazoles and their use for controlling animals pests.
Khim. Geterotsikl. Soedin., 1970 (7), 894-897 describes 3-(2-thienyl)-5-methylpyrazole, 3-(2-thienyl)-5-n-butylpyrazole and 3-(2-thienyl)-5-n-pentylpyrazole; U.S. Pat. No. 2,630,437 describes 3-(2-thienyl)-5-hydroxypyrazole; Zh. Org. Khim., 15 (1), 57-63, 1979 describes 3-(2-thienyl)-5-phenyl-1H-pyrazole; J. Electron Spectrosc. Relat. Phenom. 31 (4), 317-21, 1983 describes 3-(2-thienyl)-5-(4-methoxyphenyl)-1H-pyrazole. None of these publications, however, describes or suggests that the above-mentioned pyrazole derivatives have nematicidal activity.
Further, WO 87/06429 discloses certain kinds of insecticidal oxazole or thiazole derivatives and WO 86/05949 discloses certain kinds of insecticidal bithienyl derivatives.
It has now been found that a group of thienyl-pyrazoles of the following formulae (Ia) and (Ib) can be used for controlling animal pests. They exhibit a particularly high nematicidal activity.
Therefore, the present invention provides compounds of the formulae (Ia) and (Ib)
wherein
R
1
represents C
1-10
alkyl which may be unsubstituted or substituted with halogen, or represents hydroxy, C
2-4
alkoxyalkyl, C
2-4
hydroxyalkyl, C
3-6
cycloalkyl, hydroxy, C
1-9
alkoxy which may be unsubstituted or substituted with halogen, or represents C
3-6
cycloalkoxy, C
2-4
alkoxyalkoxy or C
3-4
alkinyloxy,
R
2
represents hydrogen, C
1-4
alkoxycarbonyl, C
1-3
alkylcarbonyl or C
2-4
alkoxyalkyl
and their use for controlling animal pests.
In case R
2
represents hydrogen, the formula (Ia) and the formula (Ib) are tautomers.
In case R
2
represents another group than hydrogen, the formula (Ia) and the formula (Ib) are regio isomers.
Each of the isomers of the above-mentioned formulae (Ia) and (Ib) can exist and can be used according to the present invention in a substantially pure form or as a mixture of different ratios.
The compounds of the formulae (Ia) and (Ib), excluding the cases in which R
1
represents methyl, n-butyl, n-pentyl or hydroxy and R
2
represents hydrogen, are novel compounds which were not described in the literature up to the present.
The thienyl-pyrazoles of the formula (Ia) and formula (Ib), wherein R
1
represents methyl, n-butyl, n-pentyl or hydroxy and R
2
represents a hydrogen, are described in Khim. Geterotsikl. Soedin., 1970 (7), 894-897 and U.S. Pat. No. 2,630,437.
Furthermore, it has been found that
(A) the compounds of the formula (Ia) and formula (Ib) wherein
R
2
represents C
1-10
alkyl which may be unsubstituted or substituted with halogen, or represents C
2-4
alkoxyalkyl, C
2-4
hydroxyalkyl or C
3-6
cycloalkyl, and
R
2
represents hydrogen
can be obtained when compounds of the formula (II)
wherein
R
1a
represents C
1-10
alkyl which may be unsubstituted or substituted with halogen, or represents C
2-4
alkoxyalkyl, C
2-4
hydroxyalkyl or C
3-6
cycloalkyl,
are reacted with hydrazine hydrate, if appropriate, in the presence of one or more inert diluents,
(B) the compounds of the formula (Ia) and the formula (Ib) wherein
R
2
represents C
1-9
alkoxy which may be unsubstituted or substituted with halogen, C
3-6
cycloalkoxy, C
2-4
alkoxyalkoxy or C
2-3
alkynyloxy, and
R
2
represents hydrogen
can be obtained when
5-hydroxy-3-(2-thienyl)pyrazole of the formula (III)
is reacted with compounds of the formula (IV)
R
1b
—M (IV)
wherein
R
1b
represents C
1-9
alkyl which may be unsubstituted or substituted with halogen, C
3-6
cycloalkyl, C
2-4
alkoxyalkyl or C
2-3
alkynyloxy, and
M represents halogen, methanesulfonyloxy, p-toluenesulfonyloxy or trifluoromethanesulfonyloxy,
in the presence of one or more inert diluent, and if appropriate, in the presence of an acid binder,
(C) the compounds of the formula (Ia) and formula (Ib) wherein
R
2
represents C
1-4
alkoxycarbonyl, C
1-3
alkylcarbonyl or C
2-4
alkoxyalky can be obtained when compounds of the formula (Ic)
wherein
R
1
has the same definition as aforementioned,
are reacted with compounds of the formula (V)
R
2a
—Hal (V)
wherein
R
2a
represents C
1-4
alkoxycarbonyl, C
1-3
alkylcarbonyl or C
2-4
alkoxyalkyl, and
Hal represents halogen,
in the presence of one or more inert diluents, and if appropriate, in the presence of an acid binder.
Finally, it has been found that the compounds of the formula (Ia) and formula (Ib) of the present invention have pronounced biological properties and are suitable especially for controlling animal pests. They especially show strong nematicidal activity and show good compatibility with crops. Therefore, the thienyl-pyrazoles of the formula (Ia) and formula (Ib) of the present invention are very useful as an effective agent for controlling animals pests.
In the present specification “Halogen” represents fluoro, chloro, bromo or iodo.
“Alkyl” may be straight chain or branched chain and there may be mentioned, for example, methyl, ethyl, propyl, isopropyl, n-, iso-, sec- or tert-butyl, n-, iso-, neo- or tert-pentyl, n- or iso-hexyl, heptyl, octyl, nonyl, decyl etc.
“Cycloalkyl” includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl etc.
“Alkoxy” may be straight chain or branched chain and there may be mentioned, for example, ethoxy, propoxy, iso-propoxy, n-, iso-, sec- or tert-butoxy, pentyloxy, hexyloxy etc.
“Alkoxyalkyl” is an alkoxy-substituted alkyl and there may be mentioned, for example, methoxymethyl, ethoxymethyl, propoxymethyl, isopropoxymethyl, n-, iso-, sec- or tert-butoxymethyl, n-, iso-, sec-, tert- or neo-pentoxymethyl etc.
“Alkoxyalkoxy” is an alkoxy-substituted alkoxy and there may be mentioned, for example, methoxymethoxy, ethoxymethoxy etc.
“Cycloalkoxy” includes, for example, cyclopropoxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy etc.
“Alkynyloxy” includes, for example, propargyloxy etc.
As “alkoxycarbonyl” there may be mentioned, for example, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl etc.
As “alkylcarbonyl” there may be mentioned, for example, acetyl, ethylcarbonyl etc.
Preferred substituents or ranges of the radicals listed in the formulae (Ia) and (Ib) mentioned hereinabove and hereinbelow are illustrated below.
R
1
preferably represents C
2-6
alkyl which may be unsubstituted or substituted with fluoro or chloro, or represents methoxymethyl, C
3-4
hydroxyalkyl, cyclopropyl, cyclopentyl, cyclohexyl, hydroxy, C
2-5
alkoxy which may be unsubstituted or substituted with fluoro or chloro, or represents cyclopentyloxy, cyclohexyloxy or C
2-3
alkoxyalkoxy.
R
2
preferably represents hydrogen, tert-butoxycarbonyl, C
1-2
alkylcarbonyl or C
2-3
alkoxyalkyl.
R
1
particularly preferably represents C
2-6
alkyl which may be unsubstituted or substituted with fluoro or chloro, or represents methoxymethyl, C
3-4
hydroxyalkyl, cyclopropyl, cyclopentyl, cyclohexyl, C
3-4
alkoxy which may be unsubstituted or substituted with fluoro or chloro, or represents cyclopentyloxy, cyclohexyloxy or methoxymethoxy.
R
2
particularly preferably represents hydrogen or acetyl.
R
1
very particularly preferably represents n-butyl, n-pentyl, n-hexyl, trifluoromethyl, ethoxy or methoxy.
R
2
very particularly preferably represents hydrogen, acetyl, methoxycarbonyl, t-butoxycarbonyl, ethoxymethyl or methoxymethyl.
R
1
most particularly preferably represents n-butyl or n-pentyl.
R
2
most particularly preferably represents hydrogen.
In the following the preparation processes of the compounds of the formula (Ia) and the formula (Ib) of the present invention will be described in more detail.
As the formula (Ia) and formula (Ib) are in relation as isomers as aforementioned, the final products described in the present specification will be shown in either of the formulae (Ia) and (Ib) for the sake of convenience, unless specified otherwise. It should be understood, however, that the compound can be described according to formula (Ia) or according to formula (Ib), because the co
Abe Takahisa
Gomibuchi Takuya
Narabu Shin-ichi
Otsu Yuichi
Shibuya Katsuhiko
Harmuth Raymond J.
Henderson Richard E. L.
Nihon Bayer Agrochem K.K.
Ramsuer Robert W.
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