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Chemistry of Aminoxides

Project Leader
Rosenau Thomas, Project Leader
Duration:
01.05.2001-01.05.2004
Type of Research
Basic Research

Further information: http://www.boku.ac.at/chemie/cdlab/cdlab.html

Staff
Adelwöhrer Christian, Co-worker (bis 30.11.2007)
BOKU Research Units
Division of Chemistry of Renewable Resources
Funded by
Fonds zur Förderung der wissenschaftlichen Forschung (FWF) , Sensengasse 1, 1090 Wien, Austria
Abstract
Amine oxides are multi-faceted compounds with numerous applications in synthetic organic chemistry. They serve as valuable targets or intermediates in multi-step syntheses, as protecting groups for aromatic amines, and as oxidants in transition metal catalyzed conversions. Apart from these laboratory applications, they are used on a large scale in industrial processes, as solvents for cellulose in derivatization-free fiber-making processes, and as non-ionic surfactants in detergents. Recent observations of novel reactions of amine oxides, such as autocatalytic decomposition processes and inducible degradations of amine oxides, have opened up a whole new area in amine oxide chemistry which will be exploited in this proposed project with regard to applications in synthesis and mechanistic insights.
The novel procedures to be investigated are deoxygenative demethylations of N-methyl amine oxides and deoxygenations with oxygen transfer. Mechanism and kinetics of the two underlying pathways will be comprehensively studied. Deoxygenative demethylation of tertiary N-methyl amine oxides produces the corresponding secondary amines. This process will be developed into an effective and selective N-demethylation procedure and applied in alkaloid chemistry. The deoxygenation with oxygen transfer does not only effect a simple reduction of the amine oxides, but can be used to generate secondary oxidants in situ that are otherwise difficult to produce, such as hypochlorous acid and peroxynitrous acid in organic media. The former reagent will be employed for an efficient high-yield synthesis of important novel vitamin E derivatives, such as 5-formyl-g-tocopherol, 4-oxo-a-tocopherol, 4-hydroxy-a-tocopherol and the Simon II metabolite of vitamin E. The latter oxidant will allow for the first time to study the reaction between peroxynitrous acid and tocopherols in the absence of interfering reactions with reactive nitrogen oxide species that are typical of aqueous media.
The outcome of the project is expected to considerably expand the knowledge on amine oxides and their reaction mechanisms. Direct results of the work will be an improved methodology based on the amine oxide reactions investigated, as well as novel synthetic procedures and their application in vitamin E chemistry.

Keywords
organic chemistry;
amine oxides; hypochlorous acid; N-demethylation; secondary oxidants; tocopherols;
Publications

Rosenau, T., Potthast, A., Lange, T., Hofinger, A., Kosma, P. (2001): Tocopherol derivatives oxidized at the pyran ring structure..

221st ACS National Meeting, April 1-5, 2001, San Diego, CA, Book of Abstracts, Part II, ORGN 0717

Rosenau, T., Potthast, A., Elder, T., Lange, T., Sixta, H., Kosma, P. (2002): Synthesis and oxidation behavior of 2,4,5,7,8-pentamethyl-4H-1,3-benzodioxin-6-ol, a multi-functional oxa-tocopherol type antioxidant..

223rd ACS National Meeting, April 7-11, 2002, Orlando, FL, Book of Abstracts, ORGN 19

Rosenau, T., Potthast, A., Hofinger, A., Gille, L., Kosma, P. (2002): Synthesis and Oxidation Behavior of a "Siamese Twin" Vitamin E Model Compound..

223rd ACS National Meeting, April 7-11, 2002, Orlando, FL, Book of Abstracts, CELL 20

** Rosenau, T., Potthast, A., Hofinger, A., Sixta, H., Kosma, P. Instabilities in the System NMMO / Water / Cellulose (Lyocell Process) caused by Polonowski Type Reactions..

Holzforschung, 56, 2, 199-208 WoS

Rosenau, T., Potthast, A., Hofinger, A., Kosma, P. (2002): Calixarenartige Makrocyclen durch Oxidation phenolischer Vitamin-E-Derivate..

Angew. Chem., 114, 7, 1219-1221

** Rosenau, T; Potthast, A; Ebner, G; Hofinger, A; Kosma, P; On a novel chromanone-naphthalenetrione rearrangement related to vitamin E..

Org Lett. 2002; 4(8):1257-1258 WoS PubMed

** Rosenau, T., Potthast, A., Sixta, H. Kosma, P. Radicals derived from N-methyl-morpholine-N-oxide (NMMO): structure, trapping, and recombination reactions..

Tetrahedron, 58, 3073-3078 WoS

** Rosenau, T., Potthast, A., Adorjan, I., Hofinger, A., Sixta, H., Firgo, H., Kosma, P. Cellulose solutions in N-methylmorpholine-N-oxide (NMMO) - Degradation processes and stabilizers..

Cellulose, 9, 3-4, 283-291 WoS

** Rosenau, T., Potthast, A., Kosma, P. Studies into reactions of N-methyl-morpholine-N-oxide (NMMO) and its hydrates with cyanuric chloride..

Tetrahedron Lett., 58, 49, 9808-9815 WoS

** Rosenau, T; Potthast, A; Elder, T; Lange, T; Sixta, H; Kosma, P; Synthesis and oxidation behavior of 2,4,5,7,8-pentamethyl-4H-1,3-benzodioxin-6-ol, a multifunctional oxatocopherol-type antioxidant..

J Org Chem. 2002; 67(11):3607-3614 WoS PubMed

** Rosenau, T; Potthast, A; Elder, T; Kosma, P; Stabilization and first direct spectroscopic evidence of the o-quinone methide derived from vitamin E..

Org Lett. 2002; 4(24):4285-4288 WoS PubMed FullText FullText_BOKU

** Adelwöhrer, R., Rosenau, T., Gille, L., Kosma, P. Synthesis of novel 3-oxa-chromanol type antioxidants.

Tetrahedron, 59, 15, 2687-2691 WoS FullText FullText_BOKU

** Adelwöhrer, C,; Rosenau, T.; Binder, W.H.; Kosma, P. Novel Tocopheryl Compounds XV. One-pot Formation of Furotocopheryl Derivatives..

Tetrahedron, 59, 18, 3231-3235 WoS FullText FullText_BOKU

** Adelwöhrer, C.; Rosenau, T.; Kosma, P. Novel Tocopheryl Compounds XVI. Nitration of alpha-Tocopheryl Acetate - a Mechanistic Study.

Tetrahedron, 59, 41, 8177-8182 WoS FullText FullText_BOKU

** Rosenau, T., Potthast, A., Kosma, P. Studies on the carbenium-iminium ions derived from N-methylmorpholine-N-oxide (NMMO).

Tetrahedron, 60, 301-306 WoS FullText FullText_BOKU

** Rosenau, T; Hofinger, A; Potthast, A; Kosma, P; A general, selective, high-yield N-demethylation procedure for tertiary amines by solid reagents in a convenient column chromatography-like setup..

Org Lett. 2004; 6(4):541-544 WoS PubMed FullText FullText_BOKU

** Rosenau, T., Adelwöhrer, C., Hofinger, A., Mereiter K., Kosma, P. 3-Tocopherylisoxazolines by [2+3] cycloaddition.

European Journal of Organic Chemistry, 2004, 1323-1329 WoS FullText FullText_BOKU

** Gregor, W; Adelwöhrer, C; Rosenau, T; Grabner, G; Gille, L Antioxidant properties of chromanols derived from vitamin E and ubiquinone..

Ann N Y Acad Sci. 2004; 1031:344-347 WoS PubMed FullText FullText_BOKU

** Adelwöhrer, C., Rosenau, T. Novel tocopherol compounds XX. 1,3,8-Trioxaphenanthrenes derived from g-tocopherol.

Tetrahedron, 61, 38, 9070-9074 WoS FullText FullText_BOKU

Adelwöhrer, C. (2004): Untersuchungen zur Chemie von phenolischen Antioxidantien.

Dept. f. Chemie/BOKU, 98; Wien

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