Drug – bio-affecting and body treating compositions – Designated organic active ingredient containing – Having -c- – wherein x is chalcogen – bonded directly to...
Reexamination Certificate
2000-04-20
2002-04-16
Rotman, Alan L. (Department: 1625)
Drug, bio-affecting and body treating compositions
Designated organic active ingredient containing
Having -c-, wherein x is chalcogen, bonded directly to...
C514S351000, C546S296000, C546S300000, C546S302000
Reexamination Certificate
active
06372766
ABSTRACT:
This application is a 371 of PCT/EP98/06683 Oct. 21, 1998.
The present invention relates to substituted 2-(2′-pyridyloxy)phenylacetamides of the formula I,
where
R
1
is fluorine, chlorine, CH
3
or halomethyl;
R
2
is fluorine, bromine, C
1
-C
4
-alkyl or halomethyl;
R
3
is hydrogen or one of the radicals mentioned under R
2
; or
R
2
is 6-chloro if R
3
is hydrogen,
R
3
is 5-chloro if R
2
is fluorine,
and the compound in which R
1
, R
2
and R
3
are each chlorine;
with the proviso that R
1
may not be chlorine if R
2
is 5-trifluoromethyl and R
3
is hydrogen.
Furthermore, the invention relates to processes for preparing the compounds I, and to compositions and to the use of the compounds I for controlling harmful fungi and animal pests.
&agr;-Phenyl-&agr;-alkoximinoacetamides having heteroaryloxy groups in ortho position are disclosed in EP-A 398 692, EP-A 629 609 and EP-A 760 363. The compounds described in the abovementioned publications are suitable for use as crop protection agents in harmful fungi, and some of them for use as bactericides.
However, their activity is not always entirely satisfactory. It is an object of the present invention to provide compounds having improved activity.
We have found that this object is achieved by the phenylacetic acid derivatives of the formula I. Furthermore, we have found processes for preparing the compounds I, and the use of the compounds I and of compositions comprising them for controlling harmful fungi and animal pests. Preference is given to the fungicidal activity.
The compounds of the formula I differ from the compounds known from the abovementioned publications in the substitution of the 2-pyridinyloxy group which has to be substituted in position 3 by the radical R
1
which has a particular structure, and unsubstituted in position 4. The compounds of the formula I have improved activity against harmful fungi and animal pests in comparison with the prior art compounds.
The compounds of the formula I can be obtained by methods similar to those described in EP-A 760 363.
In particular, the compounds of the formula Ia are obtained by the following synthetic route:
The condensation of the benzyl alcohol of the formula IIa with 2-halopyridines of the formula IIIa in which [Hal] is halogen, for example chlorine or bromine, is carried out under conditions known per se [cf. EP-A 760 363; EP-A 398 692].
2-Halopyridines of the formula IIIa are either commercially available, or they can be prepared by methods known from the literature [cf. U.S. Pat. No. 4,279,913; U.S. Pat. No. 4,491,468; JP-A 58/206 563; J. Org. Chem. (1989), p. 1726ff.].
2-Halopyridines of the formula IIIa are also obtainable from the 2-hydroxypyridines of the formula IIIb′ by halogenation, for example using POCl
3
. The halogenation is carried out under known conditions [cf. Houben-Weyl, Methoden der Organischen Chemie, Vol. 5/3, 4th Edition, p. 924ff., Thieme Verlag Stuttgart and New York (1962)].
The benzyl alcohol of the formula hIa is also known from the literature and can be obtained under known conditions [cf. EP-A 398 692].
The compounds of the formula Ib are obtained in a particularly advantageous manner via the corresponding esters of the formula IV, by the following synethic route:
The condensation of the benzyl bromide of the formula IIb with 2-hydroxypyridines of the formula IIIb is carried out under conditions known per se [cf. DE-A 38 35 028].
The benzyl bromide of the formula IIb is also known from the literature and can be obtained under known conditions [cf. EP-A 420 091; DE-A 39 17 351].
2-Hydroxypyridines of the formula IIIb are either commercially available or they can be obtained by methods similar to those known from the literature. 2-Hydroxypyridines in which R
1
, R
2
or R
3
are CF
3
are preferably obtained from the commerically available 2-hydroxypyridinecarboxylic acids IIIc by reaction with hydrogen fluoride and sulfur tetrafluoride [cf. DE-A 3 620 064].
Compounds IIIb in which R
1
is CF
3
are, for example, obtained from 2-hydroxypyridine-3-carboxylic acids of the formula IIIc by the following reaction:
2-Hydroxypyridinecarboxylic acids IIIc are also known from the literature [cf. EP-A 225 172; U.S. Pat. No. 4,960,896; U.S. Pat. No. 5,034,531], or they can be prepared by methods similar to those in the literature quoted.
The amidation of the esters of the formula IV is preferably carried out under known conditions using methylamine [cf. EP-A 398 692].
Owing to their C═N double bonds, the compounds I can be obtained in the preparation as E/Z isomer mixtures which can be separated into the substantially pure individual compounds in a customary manner, for example by crystallization or chromatography.
However, if isomer mixtures are obtained in the synthesis, a separation is generally not necessarily required since in some cases the individual isomers can be converted into each other during preparation for use or upon use (for example under the influence of light, acids or bases). Corresponding conversions may also occur after the application, for example in the treatment of plants, in the treated plant or in the harmful fungi or animal pest to be controlled.
With regard to the C═N—OCH
3
double bond, preference is given to the E isomers of the compounds I with respect to their activity (configuration based on the OCH
3
group in relation to the CONHCH
3
group).
In the definitions of the symbols given in the above formulae, collective terms were used which generally represent the following substituents:
C
1
-C
4
-Alkyl: saturated, straight-chain or branched hydrocarbon radicals having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl and 1,1-dimethylethyl;
Halomethyl: methyl groups in which some or all of the hydrogen atoms may be replaced by halogen atoms, for example chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl and chlorodifluoromethyl.
With regard to the intended use of the pyridineoxyamides [sic] of the formula I, particular preference is given to the following meanings of the substituents, in each case either alone or in combination:
Preference is given to compounds Ia in which R
1
is methyl.
Likewise, particular preference is given to compounds Ia in which R
2
is trifluoromethyl.
Additionally, particular preference is given to compounds Ia in which R
1
is fluorine or chlorine.
Especially preferred are also compounds Ia in which R
1
is trifluoromethyl.
Furthermore, particular preference is given to compounds Ia in which R
1
is C
1
-C
4
-alkyl.
Especially preferred are compounds Ia in which R
2
is fluorine or bromine.
Furthermore, particular preference is given to compounds Ib in which R
1
is trifluoromethyl.
Furthermore, particular preference is given to compounds Ib in which R
1
is fluorine or chlorine.
Likewise, particular preference is given to compounds Ib in which R
2
is trifluoromethyl.
Moreover, particular preference is given to compounds Ib in which R
3
is hydrogen.
Additionally, particular preference is given to compounds Ib in which R
2
is chlorine and R
3
is hydrogen.
Furthermore, particular preference is given to compounds I in which R
1
is fluorine, chlorine, CH
3
or CF
3
; R
2
is fluorine, bromine, C
1
-C
4
-alkyl or CF
3
; R
3
is hydrogen or one of the radicals mentioned under R
2
.
Especially preferred are the 2-(2′-pyridyloxy)phenylacetamides of the formula Ia, in particular the compounds listed in Table A below:
TABLE A
No.
R
1
R
2
A-1
methyl
trifluoromethyl
A-2
fluoro
trifluoromethyl
A-3
methyl
difluoromethyl
A-4
fluoro
difluoromethyl
A-5
chloro
difluoromethyl
A-6
methyl
fluoro
A-7
fluoro
fluoro
A-8
chloro
fluoro
A-9
methyl
bromo
A-10
fluoro
bromo
A-11
chloro
bromo
A-12
trifluoromethyl
trifluoromethyl
A-13
trifluoromethyl
fluoro
A-14
trifluoromethyl
bromo
A-15
trifluoromethyl
methyl
A-16
triflu
Ammermann Eberhard
Bayer Herbert
Gewehr Markus
Götz Norbert
Grammenos Wassilios
Keil & Weinkauf
Rotman Alan L.
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