DANNENBERG and HEBENBROCK obtained a fluorescent hydrocarbon, C
27H
34, by refluxing vitamin D
3 with chloranil in anisole (bp 155.5°C) for 1 hr (35% yield), to which a structure possessing the styryl indene chromophore was assigned (
1). During the course of our study on a fluorometric determination of vitamin D, we found this reaction to be unsuited for analytical purposes mainly because of its drastic reaction condition. We wish to report a very easy method of aromatization of vitamin D under extremely mild reaction conditions, and to emphasize the biosynthetic significance of this reaction.
Treatment of vitamin D
2 (I) in acetone with an equimolar amount of N-bromosuccinimide at room temperature for a period of 10 min led to a complete disappearance of the initial vitamin. Extraction of the diluted aqueous acetone solution with
n-hexane gave a reaction mixture consisting principally of the two fluorescent components A and B, in approximately 3:1 proportion (
2) as estimated by NMR (
3). No other reaction products were detected on gas chromatographic tracings (
4). Successive column chromatographic separation on silica gel, using
n-hexane, afforded the ingredient A in a pure state (
5). On the basis of the following data and of a comparative examination with the known vitamin isomers such as isovitamin D
2 (II) and isotachysterol
2 (III), the structure (IV) has been determined unequivocally for the compound A, and (V) was assigned tentatively to the compound B.
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