Rearrangements and Hydration of 2-Ethynylisoborneol and 2-Ethynylisocamphanol |
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Authors: | S S Koval’skaya N G Kozlov E A Dikusar |
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Institution: | 1.Institute of Physical Organic Chemistry,National Academy of Sciences of Belarus,Minsk,Belarus |
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Abstract: | The reaction of 2-ethynylisoborneol with acetic acid in the presence of boron trifluoride-diethyl ether complex gave 4-ethynylisobornyl
acetate as a result of successive skeletal rearrangements. Under the Kucherov reaction conditions 2-ethynylisoborneol underwent
Meyer—Schuster rearrangement leading to (2-bornylidene)acetaldehyde. The hydration product of 2-ethynylisoborneol, 2-acetylisoborneol,
was obtained by the action of mercury(II) acetate in dioxane under mild conditions. The Nieuwland reaction of 2-ethynylisoborneol
afforded 4-acetylisoborneol acetate. 2-Ethynylisocamphanol in the presence of formic acid gave rise to a mixture of Rupe and
Meyer—Schuster rearrangement products, stereoisomeric 2-(isocamphylidene)acetaldehydes and 2-acetylisocamphene. Mixtures of
acetyl-substituted acetates having a camphane, isocamphane, and bicyclo3.2.1]octane skeleton were obtained in the reaction
with acetic acid in the presence of BF3-Et2O. Under the Nieuwland reaction conditions 2-ethynylisocamphanol underwent hydration and rearrangement with ring expansion,
yielding a mixture of endo-2-hydroxy-2,6,6,7-tetramethylbicyclo3.2.1]octan-3-one and the corresponding acetate. |
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