Organic compounds -- part of the class 532-570 series – Organic compounds – Amino nitrogen containing
Patent
1995-06-06
1997-11-04
O'Sullivan, Peter
Organic compounds -- part of the class 532-570 series
Organic compounds
Amino nitrogen containing
558422, 564353, C07C20962, C07C25154, C07C25330, C07C25562
Patent
active
056842007
DESCRIPTION:
BRIEF SUMMARY
This application is a 371 of PCT/EP93/03597, filed Dec. 17, 1993.
The present invention relates to a process for the preparation of hydroxylamine ethers of the formula I ##STR5## in which the variables have the following meaning: X is nitro, cyano, halogen, C.sub.1 -C.sub.4 -alkyl and C.sub.1 -C.sub.4 -haloalkyl, -C.sub.4 -haloalkyl, from one to three C.sub.1 -C.sub.3 -alkyl groups, and their salts with mineral acids or strong organic acids.
The present invention furthermore relates to novel oximino derivatives of the formula IVa ##STR6## in which the variables have the following meaning: R.sup.1 is C.sub.1 -C.sub.4 -alkyl, -haloalkyl, nitro, cyano or C.sub.1 -C.sub.4 -alkoxy and 2 or 3 when Y is hydrogen, and from one to three C.sub.1 -C.sub.3 -alkyl groups, and, when R.sup.1 and R.sup.2 are both methyl, Alk is --(CH.sub.2).sub.3 -- and X.sub.n is 2,5--Cl.sub.2, Y cannot be chlorine.
The preparation of the compounds I cannot be carried out by direct O-alkylation of hydroxylamine but requires the use of methods involving protective groups. Such methods for the synthesis of hydroxylamine ethers of the type comprising the compounds I are described, for example, in Houben-Weyl, Methoden der organischen Chemie, Volume E16a, 1990, page 214 et seq. This publication also discloses the so-called N-hydroxyphthalimide method, by means of which hydroxylamine ethers of the type of the compounds I have been prepared to date according to EP-A 456 112, DE-A 42 04 203 and DE-A 42 04 206. However, this method has disadvantages for industrial use. Thus, the elimination of the protective group results not only in the desired O-substituted hydroxylamines but as a rule also in useless coupling products, for example phthalic hydrazide in the cleavage with hydrazine. Recovery of the protective group used is usually also impossible.
J. Agric. Food Chem. 38 (1990), 514 discloses the preparation of acetone tert-butylate in dioxane as a solvent. However, the process described is not suitable for an industrial preparation of the oximino derivatives IV, since large amounts of solvents are consumed. A corresponding reaction with smaller amounts of solvents is impossible since in this case viscous emulsions are obtained.
A further publication (J. Am. Chem. Soc. 74 (1952), 3956) describes the condensation of, inter alia, 2-phenoxyethyl bromide with the sodium salt of acetone oxime (although no information is given concerning the process conditions) and the cleavage of the resulting oxime ether with hydrochloric acid.
In DE-A 26 51 083, DE-A 26 51 085 and JP-A91/258 757, relatively expensive bases which are technically difficult to handle, such as alkali metal hydrides, for example sodium hydride, alkali metal amides, for example sodium amide, or organometallic compounds, for example butyllithium, are used in alkylation reactions with hydroximino derivatives of the type comprising the compounds II. These reactions must be carried out under anhydrous conditions, which is technically complicated.
Some of the oximino derivatives IV have already been disclosed in U.S. Pat. No. 4,647,698 (cf. formula (B) of the patent), as pesticides. The patent states that sodium hydride is present as the base for the preparation of said oximino derivatives from hydroximino compounds II and alkylating agents of the type comprising the compounds III. The disadvantage here is the technically complicated procedure under an inert gas.
According to Bioorg. Khim. 12 (1986), 1662, 1-(1-ethoxyethylideneaminoxy)-2-phenoxyethane can be obtained by reacting 1-(1-ethoxyethylideneaminoxy)-2-bromoethane with sodium phenolate in methanol. However, the disadvantage here is that the first-mentioned reactant is obtainable in a yield of only 28% and that the product itself is formed in a yield of only 40%.
Furthermore, it can be taken from EP-A 023 560 that certain ketoximes can be reacted with (cyclo)alkyl or arylalkyl halides to give O-substituted ketoximes. The publication does not mention the use of sulfonic esters of the type comprising the compounds III as alkylating agen
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Houben-Weyl , Methoden der organischen Chemie, vol. E16a, 4th Edition, 1990, pp. 214-250.
Bioorg. Khim., vol. 12, 1986, pp. 1662-1675.
Heterocycles, vol. 20, No. 5, 1983, Bajwa et al., pp. 839-843.
J. Am. Chem. Soc., vol. 74, 1952, pp. 3956-3957.
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Goetz Norbert
Harreus Albrecht
Klein Ulrich
Maywald Volker
Misslitz Ulf
BASF - Aktiengesellschaft
O'Sullivan Peter
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