Preparation and uses of hydrocarbylnitrones

Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...

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564248, 564271, 564272, 564275, 564278, C07D26304, C07C24902, C07C24900

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059986271

ABSTRACT:
Nitrones are produced by reaction of primary amine with aldehyde or ketone, in the presence of a transition metal-containing oxidation catalyst, and a peroxidic compound. The nitrone can then be reacted with a vinylaromatic compound to produce a 2-hydrocarbyl-5-arylisoxazolidine. Both such reactions can be conducted concurrently by including the vinylaromatic compound in the initial reaction mixture. Hydrogenation of the 2-hydrocarbyl-5-arylisoxazolidine, e.g., using hydrogen and a palladium-carbon catalyst, forms an N-hydrocarbyl-3-aryl-3-hydroxypropylamine. Such reactions enable, inter alia, synthesis of the racemic hydrochloride salt of N-methyl-3-phenyl-3-[4-trifluoromethyl)phenoxy]-propylamine, known generically as fluoxetine hydrochloride, a widely used antidepressant.

REFERENCES:
Mitsui, et al., "Tungstate Catalysed Oxidation of Secondary Amines with Hydrogen Peroxide. A Novel Transformation of Secondary Amines into Nitrones", J. Chem. Soc., Chem. Commun., 1984, pp. 874-875.
Murahashi, et al., "Tungstate-Catalyzed Oxidation of Secondary Amines to Nitrones. .alpha.-Substitution of Secondary Amines via Nitrones", J. Org. Chem., 1990, vol. 55, pp. 1736-1744.
Katritzky, et al., "The conversion of primary amines into nitrones: an extension of the Krohnke reaction", Journal of the Royal Netherlands Chem. Soc., vol. 102/1, 1983, pp. 51-54.
S. Wawzonek et al., "Intermediates in the reaction of Grignard reagents with nitromethane", Journal of Organic Chemistry, vol. 38, No. 16, 1973 pp. 2763-2766.
S. Sakaue et al., "Oxidation of aliphatic and aromatic amines with hydrogen peroxide catalyzed by peroxoheteropoly oxometalates", Chemistry Letters, 1992 pp. 289-292.

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