Drug – bio-affecting and body treating compositions – Designated organic active ingredient containing – Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
2001-04-02
2003-03-25
Coleman, Brenda (Department: 1624)
Drug, bio-affecting and body treating compositions
Designated organic active ingredient containing
Heterocyclic carbon compounds containing a hetero ring...
C514S211010, C514S360000, C540S544000, C544S065000, C548S124000
Reexamination Certificate
active
06537989
ABSTRACT:
The present invention relates to azadioxacycloalkenes of the formula I
in which the substituents R
1
to R
5
and A, the index n and the bridge member W have the following meanings:
R
1
is C
1
-C
4
-alkyl, halogen, cyano, C
1
-C
4
-haloalkyl, C
3
-C
6
-cycloalkyl;
R
2
is C
1
-C
4
-alkyl, C
1
-C
4
-haloalkyl, C
3
-C
4
-alkenyl, C
3
-C
4
-haloalkenyl, C
3
-C
4
-alkynyl or C
3
-C
4
-haloalkynyl;
R
3
is hydrogen, C
1
-C
4
-alkyl, C
1
-C
4
-haloalkyl or unsubstituted or substituted phenyl;
R
4
is ═CR
a
R
b
, —CR
d
═CR
a
R
b
or ═N—OR
c
, where
R
a
, R
b
, R
d
independently of one another are each hydrogen, halogen, C
1
-C
6
-alkyl, C
1
-C
4
-haloalkyl or unsubstituted or substituted phenyl and
R
c
is one of the radicals mentioned under R
2
;
R
5
is nitro, cyano, halogen, C
1
-C
6
-alkyl or in the case that n is greater than 1, is additionally a bridge which is attached to two adjacent ring atoms and which contains three or four members selected from the group: 3 or 4 carbon atoms, 2 or 3 carbon atoms and 1 or 2 nitrogen atoms, oxygen atoms and/or sulfur atoms, where this bridge, together with the ring to which it is attached, may form a partially unsaturated or aromatic radical and where furthermore the carbon atoms of the bridge may be partly or fully substituted by halogen atoms or methyl groups.
n is 0, 1, 2, 3 or 4, where the substituents R
5
may be different if n is greater than 1;
X is C
1
-C
4
-alkoxy-N═, C
1
-C
4
-alkoxy-CH═ or R
6
-CH═, where
R
6
is halogen, C
1
-C
4
-alkyl, C
1
-C
4
-alkylthio, C
1
-C
4
-alkylamino or di-C
1
-C
4
-alkylamino and
W is C
1
-C
3
-alkylene which is unsubstituted or mono- or disubstituted by R
7
, where
R
7
is halogen, cyano, C
1
-C
4
-alkyl, C
1
-C
4
-haloalkyl, C
2
-C
4
-alkenyl, C
2
-C
4
-haloalkenyl, C
2
-C
4
-alkynyl or C
2
-C
4
-haloalkynyl, C
1
-C
4
-alkoxy, C
1
-C
4
-haloalkoxy, C
2
-C
4
-alkenoxy, C
2
-C
4
-haloalkenoxy, C
2
-C
4
-alkynoxy or C
2
-C
4
-haloalkynoxy, C
1
-C
4
-alkylcarbonyloxy.
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.
Azadioxacycloalkenes having a (Het)aryloxy group in the ortho position are disclosed in the documents WO 95/04728 and WO 97/27189.
&agr;-phenylacrylic acid derivatives and &agr;-phenyl-&agr;-methoximino acetic acid derivatives having a bisoxime ether grouping in the ortho position are described in WO 95/21153, WO 95/18789, and those having a trisoxime ether grouping are described in WO 97/15552.
WO 97/00866, finally, discloses azadioxacycloalkenes having an &agr;-bisoxime ether grouping in the ortho position. In contrast to the compounds known from WO 97/00866, the azadioxacycloalkenes of the invention have an alkenyl or an alkoxyiminoalkyl substituent at the terminal oxime carbon atom of the &agr;-bisoxime ether grouping.
The compounds described in the abovementioned publications are suitable for use as crop protection agents against harmful fungi and in some cases against animal pests.
However, in many instances their activity is unsatisfactory.
It is an object of the present invention to provide compounds having improved activity.
We have found that this object is achieved by the azadioxacycloalkenes of the formula I mentioned at the outset. 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 I can be obtained in a variety of ways, and it is immaterial for the synthesis whether a) the azadioxacycloalkene ring (see Scheme 1) or b) the &agr;-bisoxime ether grouping in the ortho position is synthesized first.
a) Compounds of the formula I are obtained, in particular, by reacting a benzyl compound of the formula II in which the radicals R
5
, X and W are each as defined in claim 1 and L is a nucleophilically replaceable group, such as halide, C
1
-C
4
-alkylsulfonate, C
1
-C
12
-alkylphenylsulfonate or mono-C
1
-C
4
-alkyl sulfate, with an &agr;-bisoxime of the formula III in which the substituents R
1
to R
4
are each as defined in claim 1, if appropriate in the presence of a base (see Scheme 1).
The benzyl compounds II can be prepared by syntheses known from the literature [cf. WO 95/04728 and WO 97/00866]. In the formula II, L is a nucleophilically replaceable group, for example halide, such as fluoride, chloride, bromide or iodide, in particular chloride or bromide, C
1
-C
4
-alkylsulfonate, such as, for example, mesylate, C
1
-C
12
-alkylphenyl sulfonate, such as, for example, tosylate, or mono-C
1
-C
4
-alkyl sulfate, such as, for example, methyl sulfate.
The oximes of the formula III are also known from the literature [cf. WO 97/15552] or they can be prepared by methods known from the literature [cf. WO 95/21153].
The benzyl compound II is reacted with the &agr;-bisoxime III in a manner known per se, at from −10° C. to 100° C., preferably from 10° C. to 85° C., in an inert organic solvent in the presence of a base [cf. WO 97/02255].
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, alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, and also dimethyl sulfoxide, dimethylformamide, dimethylacetamide and particularly preferably tetrahydrofuran, acetonitrile or dimethylformamide. It is also possible to employ mixtures of the abovementioned solvents.
Suitable bases are, in general, 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 hydrides, such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, alkali metal and alkaline earth metal carbonates, such as lithium carbonate, potassium carbonate and calcium carbonate, and also alkali metal bicarbonates, such as sodium bicarbonate, alkali metal and alkaline earth metal alkoxides, such as sodium methoxide, sodium ethoxide, potassium ethoxide, potassium tert-butoxide and dimethoxymagnesium, furthermore organic bases, for example tertiary amines, such as trimethylamine, triethylamine, diisopropylethylamine and N-methylpiperidine, pyridine, substituted pyridines, such as collidine, lutidine, and 4-dimethylaminopyridine, and also bicyclic amines. Particular preference is given to sodium hydride, potassium carbonate, sodium ethoxide and potassium tert-butoxide.
The bases are generally employed in catalytic amounts, but it is also possible to employ them in equimolar amounts, in excess or, if appropriate, as solvent.
The starting materials are generally reacted with one another in equimolar amounts. In terms of yield, it may be advantageous to employ an excess of III, based on II.
b) A further advantageous way for preparing the compounds I (see Scheme 2) starts with &agr;-bisoxime (mono)benzyl ethers of the formula IV in which R
1
to R
5
and X are as defined in claim 1 and Y is halogen, alkylcarbonyloxy, OH, NH
2
, C
1
-C
4
-alkoxy, unsubstituted or substituted phenoxy (such as, for example, p-nitrophenoxy or pentafluorophenoxy), C
1
-C
4
-alkylamino, di-C
1
-C
4
-alkylamino or an active ester, such as succinimidoxy or isourea. The compounds IV are reacted with hydroxylamine or its acid addition salt, if appropriate in the presence of a base or a dehydrating agent, such as N,N′-dicyclohexylcarbodiimide, and a compound L
1
—W—L
2
in which W is as defined in claim 1 and L
1
and L
2
are each a nucleophilically replaceable group, such as halide, C
1
-C
4
-alkylsulfonate, C
1
-C
12
-alkylphenylsulfonate or mono-C
1
-C
4
-alkyl sulfate, or L
1
and L
2
together are a bridge —O—.
The &agr;-bisoxime (mono)benzyl
Ammermann Eberhard
Bayer Herbert
Cullmann Oliver
Gewehr Markus
Grammenos Wassilios
BASF - Aktiengesellschaft
Coleman Brenda
Keil & Weinkauf
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