Organic compounds -- part of the class 532-570 series – Organic compounds – Amino nitrogen containing
Patent
1990-09-12
1992-02-11
Bond, Robert T.
Organic compounds -- part of the class 532-570 series
Organic compounds
Amino nitrogen containing
540 29, 546184, 546188, 548216, 548531, 548537, 564297, 564299, 25218212, C07C28304
Patent
active
050877526
ABSTRACT:
The subject invention relates to a method of synthesizing nitroxides from secondary amines. This method uses a suitable dioxirane compound such as dimethyldioxirane (DMD), which is relatively stable and simple to synthesize, as the oxidizing agent. A quantity of a secondary amine having no hydrogen atoms directly attached to the alpha carbon atoms is mixed with a 2x molar ratio of the dioxirane. In a first reaction, the secondary amine is oxidized to form a hydroxylamine; in a second reaction, the hydroxylamine is further oxidized to form a nitroxide. When the dioxirane loses an oxygen atom it converts into a ketone; for example, dimethyldioxirane is converted into acetone. This is very convenient, since the ketone byproduct is a solvent that can be easily removed after the reaction without causing interfering reactions. This method provides a simple, highly selective, rapid reaction with very high yields. It can be carried out in a single reaction vessel and can be used with a wide variety of secondary amines (including secondary amines having more than one amine group) to create a corresponding variety of nitroxides.
REFERENCES:
Murray, Robert W. et al., "A New Synthesis of Nitro Compounds Using Dimethyldioxirane", Tetrahedron Letters 27 (21): 2335-2336 (1986).
Rauckman, Elmer J. et al., "Improved Method for the Oxidation of Secondary Amines to Nitroxides", Synthetic Communications, 409-413 (1975).
Murray, Robert W. and Singh, Megh, "A Convenient High Yield Synthesis of Nitroxides", Tetrahedron Letters 29 (37): 4677-4680 (Oct. 1988).
Murray, Robert W. et al., "Dioxiranes: Synthesis and Reactions of Methyldioxiranes", The Journal of Organic Chemistry 50: 2847-2853 (1985).
"Nitroxide Spin Labels Biochemical Reporter Groups", 1572-1574, (1988-1989 Catalog, Aldrich Chemical Co., Milwaukee, WI).
Murray Robert W.
Singh Megh
Bond Robert T.
Curators of the University of Missouri
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