Thesis - Open Access
Master of Science (MS)
Department / School
The failure of periodic acid to rapidly oxidize 17α-hydroxyprogesterone (I) in neutral solution prompted further inquiry into the mechanism of periodic acid oxidations. Despite the fact that periodic acid or its salts have been reported to oxidatively cleave, in good yield, compounds containing the α-keto alcohol structure such as acetoin, benzoin, benzofuroin, and diphydroxyacetone, it was reported that 20-methylpregnane-3β,17β,20,21-tetrol (II) was oxidized to pregnane-3β,17β-diol-20-one (III). This product (III) was isolated from the reaction mixture, in a high yield, suggesting that it was relatively inert to further oxidation. Pinacol, which is a glycol that contains the hydroxyl groups bonded to contiguous tertiary carbon atoms, has been found to be oxidized only slowly by periodate I neutral solutions. Since the hydroxyl group in the D ring of 17α-hydroxyprogesterone (I) is attached toa tertiary carbon atom that is part of a cyclopentane ring, it was thought that possibly the presence of a tertiary carbon hydroxyl in this α-keto alcohol is responsible for the observed lower rate of oxidation in neutral solution. To test this hypothesis, it was decided to synthesize and study the mechanism of the periodic acid oxidation of (Bicyclopentyl)-1,1’-diol (IV), a relatively simple glycol containing its hydroxyl groups bonded to contiguous tertiary carbons which are part of a cyclopentane ring. It was reasoned that if this compound was found to be easily oxidized by periodic acid in neutral solution, this would indicate that the tertiary carbon hydroxyl that is part of a cyclopentane ring is not wholly responsible for inhibiting the periodate oxidation of 17α-hydroxyprogesterone (I). If (Bicyclopentyl)-1,1’-diol (IV), however, proved to be resistant to oxidation under these conditions, this would indicate that this behavior was perhaps due to the presence of this tertiary hydroxyl bonded to a cyclopentane ring.
Library of Congress Subject Headings
Includes bibliographical references
Number of Pages
South Dakota State University
Falk, Richard John, "The Mechanism of the Periodic Acid Oxidation of (Bicyclopentyl)-l,l'-dio" (1961). Electronic Theses and Dissertations. 2753.