Method of preparing benzofurandione oxime derivatives

Details Method of preparing benzofurandione oxime derivatives Method of preparing benzofurandione oxime derivatives

2001-09-26

2002-10-08

Owens, Amelia (Department: 1625)

Organic compounds -- part of the class 532-570 series

Organic compounds

Heterocyclic carbon compounds containing a hetero ring...

Reexamination Certificate

active

06462205

ABSTRACT:

The present invention relates to a novel process for preparing benzofurandioneoxime derivatives.
A process for preparing benzofurandione methyl oximes has already been described (cf. WO 95/24396). A process for preparing carbonyl compounds from oximes has been described by Grandi et al. (cf. R. Grandi et al., Synthetic Communications, 23 (16), 2279 (1993)).
However, the compounds prepared by these processes are only obtainable in moderate yields. These processes furthermore have the disadvantage that the product is obtained as a E/Z isomer mixture.
It has now been found that compounds of the formula (I)
in which
R
1
represents substituted or unsubstituted alkyl,
R
3
represents hydrogen, substituted or unsubstituted alkyl, alkoxy, halogenoalkoxy or halogen,
are obtained when compounds of the formula (II)
 in which
R
1
and R
3
are each as defined above and
R
2
represents hydrogen, or substituted or unsubstituted alkyl, are reacted with acids, or with trialkylsilyl chloride in the presence of dialkyl sulphoxide, if appropriate in a diluent and/or a solvent.
Preference is given to processes in which compounds of the formula (II) are reacted with acids.
In the reaction with a trialkylsilyl chloride in the presence of dialkyl sulphoxide, preference is given to using trimethylsilyl chloride in the presence of dimethyl sulphoxide.
For the purposes of the invention, acids are relatively highly concentrated acids, in particular mineral acids.
Preferred mineral acids are sulphuric acid, preferably 10 to 90% strength sulphuric acid, in particular half-concentrated commercial sulphuric acid, and/or phosphoric acid, preferably 20 to 95% strength phosphoric acid, in particular commercial 85% strength phosphoric acid.
Diluents and/or solvents used, by way of example and by way of preference, in the reaction of compounds of the formula (II) with acids are water; alcohols, in particular methanol; ethers, in particular dimethoxyethane, tetrahydrofuraii, methyl tert-butyl ether or tert-amyl methyl ether; alkylnitriles, in particular acetonitrile; ketones, in particular acetone, or solvent mixtures thereof, in particular alcohol/water mixtures.
When reacting compounds of the formula (II) with trialkylsilyl chloride in the presence of dialkyl sulphoxide, the diluents and/or solvents used are ethers, in particular dimethoxyethane, tetrahydrofuran, methyl tert-butyl ether or tert-amyl methyl ether; alkylnitriles, in particular acetonitrile; N-methyl-pyrrolidone; alkanecarboxylic esters, in particular acetic ester; ketones, in particular acetone, or solvent mixtures thereof.
The reaction of compounds of the formula (II) with acids is carried out in a temperature range of from 0° C. to 100° C., preferably in a temperature range of from 20° C. to 80° C.
The reaction of compounds of the fomiula (II) with trialkylsilyl chloride in the presence of dialkyl sulphoxide is carried out in a temperature range of from 0° C. to the reflux temperature of the mixture in question, preferably at reflux temperature.
The reaction of compounds of the formula (II) is carried out at atmospheric pressure, at elevated or at reduced pressure, preferably at atmospheric pressure.
The compounds of the formula (II) are employed as E/Z isomer mixtures or as pure isomers.
The compounds of the formula (I) obtainable by the process according to the invention are then obtained in the form of the isomer mixtures or in the form of pure isomers. The isomer mixtures obtained can, if appropriate, be separated into the pure isomers by customary methods, for example by chromatograipiy.
The starting materials are defined by formula (II) above.
In the definitions, R
1
, R
2
and R
3
of the formula (II) are saturated or unsaturated hydrocarbon chains, such as alkyl, alkoxy or halogenoalkoxy, in each case straightchain or branched. Alkyl in particular represents C
1
-C
4
-alkyl, in particular methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl or i-butyl. Alkoxy in particular represents C
1
-C
4
-alkyl, in particular methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, s-butoxy, t-butoxy or i-butoxy.
Preferred substituents for alkyl in the meaning of R
2
are hydroxyl, alkoxy, alkyloxycarbonyl or halogen.
Here, halogen generally represents fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, in particular fluorine or chlorine.
In the formula (II), R
1
preferably represents methyl.
In the formula (II), R
2
preferably represents hydrogen or 2-hydroxy-ethyl, in particular hydrogen.
In the formula (II), R
3
preferably represents hydrogen. FSome of the starting materials of the formula (II) are known. The compounds 2-hydroximino-3-methoximino-2,3-dihydro-benzofuran and 2-(2-hydroxyethoxyimino)-3-methoxiniino-2,3-dihydro-benzofuran used as starting materials are described in DE-A-19706399, DE-A-19706396 and EP-A-0 846 691. The compounds of the formula (II) which are not yet known can be prepared by the processes described in DE-A-19706399, DE-A-19706396 and/or EP-A-0 846 691.
All other starting materials are customary conmmercial products, or they can be prepared from these by simple processes.
Particular preference is given to processes in which compounds of the formula (II) are reacted with half-concentrated commniercial sulphuric acid and/or comnmercial half-concentrated 85% strength phosphoric acid, at temperatures of from 20° C. to 80° C.
A decisive advantage of the process according to the invention is the yield, which is increased compared with the known processes. A further advantage of the process according to the invention consists in the fact that, when isomer mixtures are used, the E isomers are formed predominantly. Moreover, it is very surprising for the person skilled in the art that the reaction of compounds of the formula (II) can be carried out in acidic medium.
The process is used for preparing important intermediates of the formula (I) which facilitates the production of known pesticides.
The examples below serve to illustrate the invention. However, the invention is not limited to the examples.
Preparation Examples for 3-Methoximino-2-oxo-2,3-dihydrobenzofuran (1)


REFERENCES:
patent: 6005104 (1999-12-01), Gallenkamp et al.
patent: 6093837 (2000-07-01), Gallenkamp et al.
patent: 6150521 (2000-11-01), Gayer et al.
patent: 0 846 691 (1998-06-01), None
patent: 93/07116 (1993-04-01), None
patent: 95/04728 (1995-02-01), None
patent: 95/24396 (1995-09-01), None
Synthetic Communications, 23(16), 1993, pp. 2279-2284, Franco Ghelfi, Romano Grandi and Ugo M Pagnoni, Carbonyl Regeneration From Oximes and Semicarbazones by Trimethylchlorosilane-Dimethylsuphoxide.
Venkateswara Rao K. et al:, “Reactivity of 2-Hydroxy-Omega-Nitroacetophenones: Synthesis of 2-Oximinocoumaranones”, Proceedings of the Indian Academy of Sciences. Section A Physical Sciences, IN, Bagalore, Bd. 83A, Nr. 6, 1976, Seiten 238-242, XP002059228.
Loth H. et al:, “Eine Neue Synthese Von 2-Acyloxyimino-Cumaranonen”, Archiv der Pharmazie, DE, VCH Verlagsgesellschaft MBH, Weinheim, Bd. 306, Nr. 2, Feb. 1, 1973, Seiten 122-126, XP002039748.

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