Durch Bromierung ausgelöste Umlagerung tertiärer Allylalkohole: Der Einfluss eines Fluor-Substituenten auf Reaktionsgeschwindigkeit und Reaktionsverlauf
✍ Scribed by Isao Nagakura; Dang Ngoc-Huê Savary; Manfred Schlosser
- Publisher
- John Wiley and Sons
- Year
- 1980
- Tongue
- German
- Weight
- 447 KB
- Volume
- 63
- Category
- Article
- ISSN
- 0018-019X
No coin nor oath required. For personal study only.
✦ Synopsis
Rearrangement of Tertiary Allyl Alcohols Induced by Bromination: The Effect of a Fluorine Substituent on the Rate and the Outcome of the Reaction
The allyl alcohol bearing a methyl and a t‐butyl group at the hydroxylated position was found to undergo a rearrangement when treated with bromine (or N‐bromosuccinimide) in an aqueous medium and to afford a product mixture containing two regioisomeric ketones and one oxirane. Introduction of an additional methyl group or a fluorine atom at the non‐terminal olefinic center led to a more selective discrimination between potential migratory groups. As the result of an exclusive t‐butyl shift only one product, a ketone, was formed in both cases. Whereas the reaction rate was only slightly affected by the additional methyl group, it was substantially decreased by the fluorine atom.