ISSN:
0018-019X
Keywords:
Chemistry
;
Organic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
In buffered 70% aqueous dioxane the cyclopropylcarbinyl (1-X), endo-cyclobutyl (2-X) and homoallylic (3-X) derivatives (X = nucleofuge) react to give the same mixture of alcohols 1-OH and 3-OH by way of a common intermediate, the symmetrical homoallylic ion 22. This follows from a study of optically active reactants 1-X and 3-X and from the deuterium scrambling pattern in the products from deuteriated 1-X, endo-2-X and 3-X. The high solvolysis rates of 3-X indicated π-bond participation in the transition state, while the high rates of 1-X and endo-2-X reflect strong σ-bond participation which is absent in exo-2-X.Prolonged heating of 1-X, endo-2-X and 3-X in formic acid leads to a degenerate rearrangement of the initially formed 3-formate. As evidenced by deuterium scrambling, carbon atoms 1, 3 and 7 eventually become positionally equivalent in the latter compound.
Additional Material:
2 Tab.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/hlca.19760590819
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