Organic compounds -- part of the class 532-570 series – Organic compounds – Carboxylic acid esters
Reexamination Certificate
2001-04-25
2002-10-22
Killos, Paul J. (Department: 1623)
Organic compounds -- part of the class 532-570 series
Organic compounds
Carboxylic acid esters
C564S134000, C564S147000
Reexamination Certificate
active
06469195
ABSTRACT:
TECHNICAL FIELD
The present invention relates to 2-phenoxyphenylacetic acid derivatives of the formula I:
where the substituents and the index have the following meanings:
A is
where
R
1
is halogen, C
1
-C
4
-alkyl, C
1
-C
4
-alkoxy, CF
3
, C
1
-C
4
-haloalkoxy, formyl, C(═O)NR
a
R
b
or C(R
a
)═NOR
b
;
R
a
is hydrogen or C
1
-C
4
-alkyl;
R
b
is C
1
-C
4
-alkyl;
n is 1, 2, 3 or 4, where the groups R
1
may be different if n is not 1;
R
2
is halogen, CH
3
or CF
3
;
m is 0 or 1; and
X is OCH
3
or NHCH
3
.
In addition, the invention relates to processes and intermediates for preparing the compounds I, and to the use of the compounds I for controlling harmful fungi.
BACKGROUND ART
2-Phenoxyphenylacetic esters are known from EP-A 253 213 and EP-A 254 426, and the corresponding amides are described in 45 EP-A 398 692 and EP-A 477 631. The compounds described in the abovementioned publications are suitable for use as crop protection agents against harmful fungi.
However, in many instances their activity is unsatisfactory.
DISCLOSURE OF INVENTION
It is an object of the present invention to provide compounds having improved activity.
We have found that this object is achieved by the 2-phenoxyphenylacetic acid derivatives of the formula I. Furthermore, we have found intermediates and processes for preparing the compounds I, and their use, and compositions comprising them for controlling harmful fungi.
The compounds of the formula I differ from the compounds known from the abovementioned publications in the specific variation of the substitution at the 2-phenoxy radical by a substituted phenyl ring in meta- or para-position and, if appropriate, a further substituent in meta- or para-position.
The compounds of the formula I can be obtained per se by the processes described in EP-A 253 213, EP-A 254 426, EP-A 398 692 and EP-A 477 631.
MODE(S) FOR CARRYING OUT THE INVENTION
In particular, the compounds of the formula I are obtained by reacting alkyl &agr;-phenyl-&agr;-ketoacetates of the formula II under basic conditions with phenols of the formula III to give alkyl &agr;-(2-phenoxyphenyl)-&agr;-ketoacetates of the formula IV. In formula II, L is a leaving group customary for nucleophilic aromatic substitution, such as halogen, in particular fluorine or chlorine, or sulfonate or nitro. This reaction is carried out under generally customary conditions, similar to WO-A 97/24317.
Keto esters IV are reacted with O-methylhydroxylamine or its acid addition salt of the formula Va, if appropriate in the presence of a base, under the conditions described in EP-A 493 711, to give oxime ethers of the formula IA.
If X in the formula I is NHCH
3
, the esters of the formula IA are converted with methylamine according to methods known from EP-A 398 692 into the amides of the formula IB.
In the formula Va, Q is the anion of an inorganic acid, in particular a halide ion.
Phenols of the formula III are known from the literature, or they can be obtained by methods known from the literature [cf.: WO-A 96/23749; WO-A 97/18188; JP-A 04/173756; JP-A 08/157406; EP-A 625 726; Synthesis (1990), 827-833].
Alternatively, the compounds of the formula I can also be obtained by the method known from WO-A 95/34526.
In a further process, compounds of the formula I can also be prepared from compounds of the formula VI by transition-metal-catalyzed coupling with a phenyl derivative of the formula VII.
In formula VII, M is an organometallic radical, such as, for example, B(OH)
2
, Sn(CH
3
)
3
, Sn(n—C
4
H
9
)
3
, Mg—Hal or Zn—Hal. In formulae VI and VII, “Hal” is a halogen atom, such as chlorine, bromine or iodine, in particular bromine and iodine.
The reaction of VI with VII is generally carried out at 10° C.-150° C., preferably at 50° C.-120° C., in an inert organic solvent [cf. WO-A 98/11070; Synth. Commun. (1981), 513; Angew. Chem. Ind. Ed. (1986), 508]. If M in the formula VII is B(OH)
2
, the reaction is carried out in the presence of a base [cf. Synth. Commun. (1981), 513; ibid (1994), 709; J. Het. Chem. (1989), 865; J. Org. Chem. (1988), 2052; ibid (1994), 6095].
Suitable solvents are ethers, such as dioxane, dimethoxyethane and tetrahydrofuran. It is also possible to use mixtures of the abovementioned solvents.
Bases which are suitable for the Suzuki reaction are, for example, potassium carbonate, sodium carbonate, sodium bicarbonate and triethylamine.
Suitable catalysts are, for example: trans-bis(acetonitrile)palladium(II) chloride, bis(dibenzylideneacetone)palladium(0), bis(triphenylphosphine)palladium(II) chloride, palladium acetate, palladium chloride and tetrakis(triphenylphosphine)palladium(0).
The compounds of the formula VI are known from EP-A 253 213, EP-A 254 426, EP-A 398 692 and EP-A 477 631, or they can be obtained by the routes described in these publications.
If individual compounds I are not obtainable by the routes described above, they can be prepared by derivatization of other compounds I.
The reaction mixtures are worked up in a customary manner, for example by mixing with water, phase separation and, if required, chromatographic purification of the crude products. Some of the intermediates and end products are obtained in the form of colorless or slightly brownish, viscous oils, which are purified or freed from volatile components under reduced pressure and at moderately elevated temperature. If the intermediates and end products are obtained as solids, purification can also be carried out by recrystallization or digestion.
Owing to their C═N double bonds, the preparation of the compounds I may yield E/Z isomer mixtures which can be separated into the individual compounds in a customary manner, for example by crystallization or chromatography.
However, if the synthesis yields isomer mixtures, a separation is generally not necessarily required since in some cases the individual isomers can be converted into one another during the preparation for use or upon use (for example under the action of light, acids or bases). Similar conversions may also occur after use, for example in the treatment of plants in the treated plant or in the harmful fungus to be controlled.
With regard to the C═NOCH
3
double bond, preference, on account of their activity, is given to the E isomers of the compounds I (configuration based on the OCH
3
group in relation to the COX group).
In the symbol definitions given in the formulae above, collective terms were used which generally represent the following substituents:
Halogen: fluorine, chlorine, bromine and iodine;
Alkyl: saturated, straight-chain or branched hydrocarbon radicals having 1 to 4 carbon atoms, for example C
1
-C
4
-alkyl, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl and 1,1-dimethylethyl;
Haloalkyl: straight-chain or branched alkyl groups having 1 to 4 carbon atoms (as mentioned above), where in these groups some or all of the hydrogen atoms may be replaced by halogen atoms as mentioned above, for example C
1
-C
2
-haloalkyl, such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl and pentafluoroethyl;
Alkoxy: straight-chain or branched alkyl groups having 1 to 4 carbon atoms (as mentioned above) which are attached to the skeleton via an oxygen atom (—O—);
Haloalkoxy: straight-chain or branched haloalkyl groups having 1 to 4 carbon atoms (as mentioned above) which are attached to the skeleton via an oxygen atom (—O—);
Alkylamino: a straight-chain or branched alkyl group having 1 to 4 carbon atoms (as mentioned above) which is attached to the skeleton via an amino group (—NH—);
Dialkylamino: two straight-chain or branched alkyl groups which are independent of one another and in each case have 1 to 4 carbon atoms (as mentioned above)
Ammermann Eberhard
Cullmann Oliver
Gewehr Markus
Götz Norbert
Götz Roland
BASF - Aktiengesellschaft
Keil & Weinkauf
Killos Paul J.
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