Bisoximether derivatives, methods and intermediate products...

Details Bisoximether derivatives, methods and intermediate products... Bisoximether derivatives, methods and intermediate products...

2000-11-02

2002-07-02

Killos, Paul J. (Department: 1614)

Drug, bio-affecting and body treating compositions

Designated organic active ingredient containing

Nitrogen containing other than solely as a nitrogen in an...

C560S035000, C560S129000, C560S157000, C562S451000, C564S167000, C564S166000, C558S389000, C514S477000

Reexamination Certificate

active

06414031

ABSTRACT:

The present invention relates to bisoxime ether derivatives of the formula I
in which the variables have the following meanings:
R
1
is halogen, C
1
-
4
-alkyl, C
1
-C
4
-haloalkyl, C
1
-C
4
-alkoxy or C
1
-C
4
-haloalkoxy;
n is 1 to 5, it being possible for the radicals R
1
to be different if n is other than 1;
R
2
is C
1
-C
4
-alkyl, C
3
-C
6
-alkenyl or C
3
-C
6
-alkynyl, it being possible for these groups to be partially or fully halogenated;
Q is C(═CHOCH
3
)—COOCH
3
, C(═CHCH
3
)—COOCH
3
, C(═NOCH
3
)—COOCH
3
or C(═NOCH
3
)—CONHCH
3
;
and to salts thereof.
Moreover, the invention relates to processes and intermediates for the preparation of these compounds and to their use for controlling animal pests and harmful fungi.
WO-A 95/18789, WO-A 95/21153, WO-A 95/21154 and WO-A 97/05103 disclose bisoxime ether derivatives for controlling harmful fungi and animal pests, but these are not always satisfactory with regard to their action.
It is an object of the present invention to provide novel compounds of this type with an improved action.
We have found that this object is achieved by the bisoxime ether derivatives I defined at the outset. Moreover, we have found processes and intermediates for their preparation, and also compositions comprising them for controlling animal pests and harmful fungi and their use for this purpose.
The compounds of the formula I differ from the compounds mentioned in the publications cited above by the design of the bisoxime ether group, which has attached to it a substituted cyclohexyl group.
The compounds I can be obtained by various routes by processes known per se.
When synthesizing the compounds I, it is, in principle, irrelevant whether it is the group —Q or the group
which is constructed first.
The construction of group —Q is disclosed, for example, in the publications mentioned at the outset and in those which follow: EP-A 254 426, EP-A 370 629, EP-A 463 488, EP-A 472 300 and EP-A 513 580.
When synthesizing the compounds I, a procedure is generally followed in which a benzyl derivative of the formula II is reacted with a hydroxyimine of the formula III
In formula II, L
1
is a nucleophilically exchangeable leaving group, for example halogen or sulfonate groups, preferably chlorine, bromine, iodine, mesylate, tosylate or triflate.
The reaction takes place in an inert organic solvent in the presence of a base, for example sodium hydride, potassium hydroxide, sodium hydroxide, sodium methoxide, sodium ethoxide, potassium carbonate or triethylamine, following the methods described in Houben-Weyl, 4th Edition, Vol. E 14b, p. 370 et seq. and ibid. Vol. 10/1, p. 1189 et seq.
The hydroxyimine III required is obtained, for example, by reacting a corresponding dihydroxyimine IV with the compound of the formula VI
In formula VI, L
2
is a nucleophilically exchangeable leaving group, for example halogen or sulfonate groups, preferably chlorine, bromine, iodine, mesylate, tosylate or triflate.
The reaction takes place in an inert organic solvent in the presence of a base, for example potassium carbonate, potassium hydroxide, sodium hydride, sodium hydroxide, sodium methoxide, sodium ethoxide, pyridine or triethylamine as described in: Houben-weyl, 4th Edition, Vol. E 14b, p. 307 et seq., p. 370 et seq. and p. 385 et seq.; ibid., 4th Edition, Vol. 10/4, p. 55 et seq., p. 180 et seq. and p. 217 et seq.; ibid., 4th Edition, Vol. E 5, p. 780 et seq.
The compounds of the formula IV can be prepared by known methods [cf. Gazz. Chim. Ital. 59 (1929), p. 719; Collect. Bull. Soc. Chim. Fr. 17 (1897), p. 71; C. R. Seances Acad. Sci. Ser. D Vol. 267 (1968), p. 579].
Alternatively, the compounds I may also be obtained by first reacting the benzyl derivative II with the dihydroxyimino derivative IV to give a corresponding benzyl oxime of the formula V, V subsequently being reacted with a compound of the formula VI to give I.
The reaction takes place in an inert organic solvent in the presence of a base, for example potassium carbonate, potassium hydroxide, sodium hydride, sodium hydroxide, sodium methoxide, sodium ethoxide, pyridine or triethylamine in accordance with the methods described in Houben-Weyl, 4th Edition, Vol. 10/1, p. 1189 et seq., Vol. E 14b, p. 307 et seq., p. 370 et seq. and p. 385 et seq., Vol. 10/4, p. 55 et seq., p. 180 et seq. and p. 217 et seq., Vol. E 5, p. 780 et seq.
Similarly, it is also possible to prepare the required hydroxyimine of the formula III from a carbonylhydroxyimine VII by reacting the latter with a hydroxylamine IXa or a salt thereof IXb.
In formula IXb, Q
⊖
is the anion of an acid, in particular of an inorganic acid, for example halide, such as chloride.
The reaction takes place in an inert organic solvent in accordance with the methods described in EP-A 513 580 and Houben-Weyl, 4th Edition, Vol. 10/4, p. 73 et seq., Vol. E 14b, p. 369 et seq. and p. 385 et seq.
The hydroxyimines of the formula VII can be obtained, for example, by the following synthetic routes [cf. J. Am. Pharm. Assoc. Vol. 35 (1946), p. 15]:
In the reaction scheme above, “Hal” is a halogen atom, in particular chlorine or bromine. The reaction of the compounds VIIa and VIIb, which follows a Grignard reaction, is carried out under generally customary conditions [cf. Organikum (Organic Chemistry), VEB Deutscher Verlag der Wissenschaften, 15th Edition, p. 617 et seq., Berlin 1981].
Oxidation of the alcohol VIIc can be effected under generally customary conditions [cf. Houben-Weyl, Methoden der organischen Chemie (Methods in Organic Chemistry), Vol. VII/2a, 4th Edition, pp. 699-776, Georg Thieme Verlag, Stuttgart 1973]. Suitable oxidants are generally oxygen-transferring compounds such as, for example, hydrogen peroxide, chromium(VI) compounds, manganese compounds, nitrogen-oxygen compounds (for example nitric acid), dimethyl sulfoxide or compounds with positively induced halogen (for example hypohalites).
Conversion of the ketone VIId into an oxime is normally carried out in an inert organic solvent in the presence of an acid or base [cf. Houben-Weyl, Methoden der organischen Chemie (Methods in Organic Chemistry), Vol. X/
4
, 4th Edition, pp. 10-27 Georg Thieme Verlag, Stuttgart 1968].
The starting materials VIIa and VIIb are known and some are commercially available.
Alternatively, the compounds I may also be obtained by first reacting the benzyl derivative II with the carbonylhydroxyimino derivative VII to give a corresponding benzyloxyimine of the formula VIII, VIII subsequently being reacted with the hydroxylamine IXa or a salt thereof IXb to give I.
The reaction is carried out in an inert organic solvent in accordance with the methods described in Houben-Weyl, Methoden der organischen Chemie (Methods in Organic Chemistry), Georg Thieme Verlag Stuttgart 1980, 4th Edition, Vol. E 14b, p. 369 et seq., Vol. 10/1, p. 1189 et seq. and Vol. 10/4, p. 73 et seq. or EP-A 513 580.
A further possibility of preparing the compounds I is to react the benzyl derivative II with N-hydroxyphthalimide and subsequently subjecting the product to hydrazinolysis to give the benzylhydroxylamine IIa, which is reacted further with a carbonyl compound X.
The reaction is carried out in an inert organic solvent in accordance with the methods described in EP-A 463 488 and EP-A 585 751.
The carbonyl compound X is obtained, for example, by reacting a corresponding hydroxyiminocarbonyl compound VIIa with a compound of the formula VI
or by reacting a corresponding dicarbonyl compound XI with a hydroxylamine IXa or a salt thereof IXb
The reactions are carried out in an inert organic solvent in accordance with the methods described in EP-A 513 580, Houben-Weyl, 4th Edition, Vol. 10/4, p. 55 et seq., p 73 et seq., p. 180 et seq. and p. 217 et seq., Vol. E 14b, p. 307 et seq. and 369 et seq., Vol. E 5, p. 780 et seq.
The compounds of the formula VIIa or XI can be prepared by known methods [cf. J. Chem. Soc. (1955), 3094; Bull. Soc. Chim. Fr. (1969), 2894; Tetrahedron 40 (1984), 2035; J. Org. Chem.

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