Organic compounds -- part of the class 532-570 series – Organic compounds – Amino nitrogen containing
Patent
1996-11-04
1998-04-14
Burn, Brian M.
Organic compounds -- part of the class 532-570 series
Organic compounds
Amino nitrogen containing
564256, 564300, 564413, C07C20952
Patent
active
057394024
DESCRIPTION:
BRIEF SUMMARY
The present application is a National Stage Application under 35 U.S.C. .sctn.371 of International Application No. PCT/EP 95/01581 filed Apr. 26, 1995.
DESCRIPTION
The present invention relates to a process for preparing mixtures of isomers of O-phenoxyalkylhydroxylamines of the formulae Ia and Ib nonaromatic substituents, and the corresponding salt mixtures.
The invention additionally relates to the preparation of mixtures of O-phenoxyalkyloximes of the formulae VIa and VIb ##STR6## where R.sup.2 is an alkyl group and R.sup.3 is an alkyl or alkoxy group, or R.sup.2 and R.sup.3 form, together with the common carbon atom, a 5- to 7-membered isocyclic ring.
Furthermore, certain novel mixtures of isomers have been found.
The earlier German Application DE-A 42 44 390 discloses the reaction of oximes with phenoxyalkylating agents in the presence of a base to give O-phenoxyalkyloximes.
Furthermore, GB-A-2 115 812 discloses a process for preparing O-phenoxyalkyloximes in which the mesylate or tosylate of an O-alkylated oxime is reacted with a phenol, using a base.
Since the direct alkylation of hydroxylamine does not as a rule take place selectively on the oxygen atom, the processes for preparing O-phenoxyalkylhydroxylamines mostly make use of protective group techniques (cf. Houberr-Weyl, Methoden der Organischen Chemie, Thieme Verlag, Stuttgart, 1990, Volume E16a/l, page 214 to page 250). In this connection, the use of N-hydroxyphthalimide as N-protected hydroxylamine has achieved particular importance. The required O-phenoxyalkylhydroxylamines are obtained starting from the latter by alkylation of the hydroxyl group and subsequent elimination of the phthalic acid moiety. This synthetic route has not, however, proven satisfactory because of the low yields and the loss of the protective group compound.
Hence, it was an object of the present invention to provide a more economic process for preparing O-phenoxyalkylhydroxylamines and O-phenoxyalkyloximes.
Accordingly, this object was achieved by a process for preparing mixtures of O-phenoxyalkylhydroxylamines of the formula I, which comprises formulae IIa and IIb ##STR7## where R.sup.2 is an alkyl group and R.sup.3 is an alkyl or alkoxy group, or R.sup.2 and R.sup.3 form, together with the common carbon atom, a 5- to 7-membered isocyclic ring, of a base into the corresponding mixture of sulfonates IVa and IVb ##STR8## b) reacting this mixture of sulfonates in the presence of a base with a phenol of the formula V ##STR9## c) hydrolyzing this mixture in the presence of an acid and, optionally, d) liberating the O-phenoxyalkylhydroxylamines Ia and Ib from the resulting salts using a mineral base.
Furthermore, a process for preparing mixtures of O-phenoxyalkyloximes of the general formulae VIa and VIb was found which comprises the abovementioned process steps a) and b),
The invention also extends to mixtures of isomers of
The process according to the invention can be illustrated in a simple case as follows: ##STR10##
With a view to the active substances which can be prepared from the products VI and I, the individual variables preferably have the following meanings, both alone and in combination: three substituents, each selected from the group consisting of nitro, cyano, halogen, C.sub.1 -C.sub.4 -alkyl or C.sub.1 -C.sub.4 -haloalkyl, particularly preferably 4-halophenyl, especially 4-chlorophenyl; 7-membered isocyclic ring.
Particularly preferred O-phenoxyalkyloximes VI are those where R.sup.1 and R.sup.2 are an C.sub.1 -C.sub.4 -alkyl group, in particular the methyl and/or ethyl group, as well as the n-propyl and the n-butyl group.
Very particularly preferred O-phenoxyalkyloximes VI are those derived from acetone O-phenoxyalkyloxime, in particular 2-propanone
Particularly preferred O-phenoxyalkylhydroxylamines I are those derived from the preferred and particularly preferred O-phenoxyalkyloximes VI as mentioned above.
The sulfonates IV can be obtained by reacting O-(2-hydroxyalkyl)oximes II with sulfonyl halides III in the presence of bases.
The O-(2-hydroxyalkyl
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Borchers Dirk
Buschulte Thomas
Gotz Norbert
Harreus Albrecht
Hartmann Horst
BASF - Aktiengesellschaft
Burn Brian M.
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