24165-02-4Relevant academic research and scientific papers
Transformation of α-tocopherol (vitamin E) and related chromanol model compounds into their phenoxonium ions by chemical oxidation with the nitrosonium cation
Lee, Stephen B.,Lin, Ching Yeh,Gill, Peter M. W.,Webster, Richard D.
, p. 10466 - 10473 (2005)
α-Tocopherol (α-TOH), the main oil component making up vitamin E, and its nonnatural solid 6-hydroxy-2,2,5,7,8-pentamethylchroman and 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid structurally related analogues were oxidized quantitatively with 2 mol equiv of NO +SbF6- in CH3CN at 233 K to form phenoxonium cations (α-TO+SbF6-) in a chemically reversible two-electron/one-proton process. Solution-phase infrared spectroscopy, 1H and 13C NMR spectroscopy, and corresponding theoretical calculations of the spectroscopic data using density-based and wave-function-based models support the identity of the remarkably stable phenoxonium cations. The presence of an oxygen atom in the para position to the hydroxyl group and the chromanol ring structure appear to be important factors in stabilization of the phenoxonium ions, which raises the interesting possibility that the cations play a crucial role in the mode of action of vitamin E in biological systems. Although the phenoxonium cations are reactive toward nucleophiles such as water, they may be moderately stable in the hydrophobic (lipophilic) environment where vitamin E is known to occur naturally.
Novel tocopheryl compounds XXV: synthesis and comparison of the para-quinones of all four homologous tocopherol model compounds and their 3,4-dehydro derivatives
Patel, Anjan,Netscher, Thomas,Gille, Lars,Mereiter, Kurt,Rosenau, Thomas
, p. 5312 - 5318 (2008/02/01)
Four tocopherol model compounds, the chroman-6-ols (1-4) having the typical substitution pattern of α-, β-, γ-, and δ-tocopherol (vitamin E), were oxidized to the corresponding para-quinones (5-8), and dehydrogenated to the 2H-chromen-6-ols (17-20) involving initial acetyl protection of the phenolic OH and deprotection as the last step. The chromenols were also converted into the para-quinones (21-24), which existed in the bicyclic hemiketal form, in contrast to the chromanol-derived, monocyclic quinones 5-8, the ketalization behavior agreeing well with computations on the DFT level.
Reactions of a Hydroperoxide, 8a-Hydroperoxy-2,2,5,7,8-pentamethylchroman-6(8aH)-one, Derived from a Vitamine E Model Compound: Dimerization and X-Ray Crystal Structure
Matsumoto, Shigenobu,Matsuo, Mitsuyoshi,Iitaka, Yoichi
, p. 601 - 641 (2007/10/02)
A hydroperoxide, 8a-hydroperoxy-2,2,5,7,8-pentamethylchroman-6(8aH)-one, was obtained from the reaction of a vitamin E model compound, 2,2,5,7,8-pentamethylchroman-6-ol, with singlet oxygen, and was dimerized in toluene in the presence of lead tetraacetate to give bis(2,2,5,7,8-pentamethyl-6-oxo-6,8a-dihydrochroman-8a-yl) peroxide.The structures of the hydroperoxide and peroxide were confirmed by X-ray crystallographic analysis, and their properties were examined.
