Drug – bio-affecting and body treating compositions – Designated organic active ingredient containing – Ester doai
Reexamination Certificate
1999-09-14
2001-02-13
Vollano, Jean F (Department: 1621)
Drug, bio-affecting and body treating compositions
Designated organic active ingredient containing
Ester doai
C514S538000, C560S035000, C564S256000
Reexamination Certificate
active
06187816
ABSTRACT:
The present invention relates to phenylketiminooxybenzyl compounds of the general formula I
where:
X is O or NH;
R
1
is fluorine, chlorine, C
1
-C
4
-alkyl, C
1
-C
4
-haloalkyl, C
1
-C
4
-alkoxy and C
1
-C
4
-haloalkoxy;
R
2
is halogen, C
1
-C
4
-alkyl, C
1
-C
4
-haloalkyl and C
1
-C
4
-alkoxy;
R
3
is halogen, C
1
-C
4
-alkyl, C
1
-C
4
-haloalkyl, C
1
-C
4
-alkoxy, C
1
-C
4
-haloalkoxy, C
3
-C
6
-cycloalkyl, phenyl or phenoxy, it being possible for each of the phenyl radicals in turn to carry one to three of the following groups: halogen, C
1
-C
4
-alkyl, C
1
-C
4
-haloalkyl, C
1
-C
4
-alkoxy and C
1
-C
4
-haloalkoxy;
CR
a
=NOR
b
, where
R
a
is hydrogen or C
1
-C
4
-alkyl and
R
b
is C
1
-C
4
-alkyl, C
3
-C
4
-alkenyl or C
3
-C
4
-alkynyl;
n is 1, 2 or 3, it being possible for the radicals R
3
to be different if n is 2 or 3,
and salts thereof.
Additionally, the invention relates to processes for preparing the compounds I and to compositions comprising them and to their use for controlling animal pests and harmful fungi.
The literature discloses active compounds whose general formula differs from the present compounds I in that the R
1
position is unsubstituted (EP-A 460 575; EP-A 585 751). Additionally, active compounds whose general formula includes the present compounds I are described in the literature (EP-A 463 488; EP-A 472 300; WO-A 92/13,830).
It is an object of the present invention to provide compounds having a broader activity spectrum and an improved activity.
We have found that this object is achieved by the compounds I defined at the outset. In addition, the invention provides processes for preparing the compounds I and compositions comprising them and their use for controlling animal pests and harmful fungi.
The present compounds I differ from the compounds known from EP-A 463 488, EP-A 472 300 and WO-A 92/13,830 in their particular combination of the groups R
1
and R
3
. Specifically, it has been found that compounds of the known structural type have improved activity when they carry one of the groups mentioned under R
1
in position 6 and the phenyl radical is additionally substituted by at least one radical R
3
which increases the lipophilicity of the compound.
In general, the compounds I can be obtained by the processes described in the literature cited at the outset.
The compounds I are particularly advantageously obtained by reacting a N-hydroxyketimine IIa in an inert solvent with a benzyl compound IIIa.
In the formula IIIa, L is a customary leaving group, for example halogen (fluorine, chlorine, bromine, iodine, in particular chlorine and bromine), C
1
-C
4
-alkylsulfonyl (in particular mesylate), C
l
-C
4
-haloalkylsulfonyl (in particular triflate) or arylsulfonyl (in particular tosylate).
The reaction of IIa with IIIa is usually carried out at from −30° C. to 120° C., preferably −10° C. to 90° C., in an inert organic solvent in the presence of a base (cf. lit. DE-A 40 20 384).
Suitable solvents are ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, and dimethyl sulfoxide, dimethylformamide and dimethylacetamide, particularly preferably tetrahydrofuran, acetonitrile, acetone and dimethylformamide. It is also possible to use mixtures of the solvents mentioned.
In general, suitable bases are inorganic compounds such as alkali metal and alkaline earth metal hydroxides, such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal oxides, such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal and alkaline earth metal hydrides, such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, alkali metal amides, such as lithium amide, sodium amide and potassium amide, alkali metal and alkaline earth metal carbonates, such as lithium carbonate, potassium carbonate and calcium carbonate, and alkali metal bicarbonates, such as sodium bicarbonate, organometallic compounds, in particular alkali metal alkyls, such as methyllithium, butyllithium and phenyllithium, alkylmagnesium halides, such as methylmagnesium chloride, and alkali metal and alkaline earth metal alkoxides, such as sodium methoxide, sodium ethoxide, potassium ethoxide, potassium tert-butoxide and dimethoxymagnesium, moreover organic bases, for example tertiary amines, such as trimethylamine, triethylamine, triisopropylethylamine and N-methylpiperidine, pyridine, substituted pyridines such as collidine, lutidine and 4-dimethylaminopyridine, and also bicyclic amines. Particular preference is given to potassium carbonate, sodium methoxide and sodium hydride.
In general, the bases are employed in catalytic amounts, but it is also possible to employ them in equimolar amounts, in an excess or, if appropriate, as solvent.
In general, the reactants are reacted with each other in equimolar amounts. To increase the yield, it may be advantageous to employ an excess of IIa, based on IIIa.
The starting materials IIa required for preparing the compounds I are known from the literature [Bull. Soc. Chim. Fr. (1899), 69; Synth Commun. (1986), 1247; J. Agric. Food Chem. (1969), 923], or they can be prepared according to the cited literature.
The starting materials of the formula IIIa where X is O are advantageously obtained by converting a 1-bromo-2-methylbenzene of the formula IV with methyl oxalyl chloride into the corresponding &agr;-ketophenylacetate of the formula V, converting V in a conventional manner with O-methylhydroxylamine into the corresponding oxime VI and finally halogenating VI to IIIa.
The reaction of IV with methyl oxalyl chloride is usually carried out from −78° C. to 80° C., preferably −10° C. to 60° C., in an inert organic solvent in the presence of an auxiliary reagent [M].
Suitable auxiliary reagents [M] are metals such as magnesium or metal organyls such as methyllithium, butyllithium and phenyllithium. Preference is given to using magnesium and butyllithium. In general, the auxiliary reagent is employed in at least stoichiometric amounts. It is preferably employed in amounts from 1 molar equivalent to 2 molar equivalents, in particular 1 molar equivalent to 1.3 molar equivalents, based on the phenyl derivative IV.
Suitable solvents are ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, particularly preferably dimethyl ether or tetrahydrofuran. It is also possible to use mixtures of the solvents mentioned.
In general, the reactants are reacted with each other in equimolar amounts. To increase the yield, it may be advantageous to employ an excess of methyl oxalyl chloride, based on IV.
The reaction of the &agr;-ketoester V with O-methylhydroxylamine is generally carried out in a customary manner at from 0° C. to 90° C., preferably 20° C. to 70° C., in an inert organic solvent; in particular, the reaction is carried out according to the conditions described in EP-A 493 711.
The halogenation of VI to IIIa is generally carried out in a conventional manner at from 0° C. to 120° C., preferably 20° C. to 110° C., in an inert organic solvent; in particular, the halogenation is carried out according to the conditions described in EP-A 385 224.
The compounds IIIa where X is NH are advantageously obtained from the corresponding esters VI by reaction with methylamine or its salt and subsequent halogenation.
The reaction of the ester to give the amide is generally carried out in a customary manner at from 0° C. to 90° C., preferably 20° C. to 70° C., in an inert organic solvent, in particular, the reaction is carried out according to the conditions described in EP-A 477 631 and DE-A 40 20 384.
The halogenation of the amides VI is generally and in particular carried out under the conditions described for the halogenation of the esters.
Compounds IIIa where L is a l
Ammermann Eberhard
Bayer Herbert
Gotz Roland
Grammenos Wassilios
Grote Thomas
BASF - Aktiengesellschaft
Keil & Weinkauf
Vollano Jean F
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