Oxygen based radicals in organic chemistry /
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| Other Authors: | |
| Format: | Thesis Book |
| Language: | English |
| Published: |
[College Station, Tex.] :
Van de Mark,
1976.
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| Subjects: | |
| Online Access: | Link to ProQuest copy Link to OAKTrust copy |
| Abstract: | The remote oxidation of unactivated carbon-hydrogen bonds by photo-excited nitrobenzene and benzophenone derivatives is described. The procedure is illustrated by the key step in the conversion of 5α-androstand-3α-of to 5α-androst-14-en-3-one. The photolysis of benzophenone solubilized in a micell produces some selectivity for the w-position in a 16 carbon micelle. The electrochemical oxidation of aliphatic alcohols has been studied. It was found that acetonitrile and fluoroborate is the best solvent electrolyte system for the direct oxidation of alcohols. The indirect oxidation of secondary alcohols was accomplished in 1:10 water: acetonitrile as the solvent and nitrate as the electro-active species. The direct oxidation of alcohols produced the respective alkoxyl radicals. With isoborneol, the radical undergoes β-fragmentation in high yields. The indirect oxidation with nitrate produced ketones in very high yield from the corresponding secondary alcohol. The mechanistic conclusions derived from these observations were; that the alkoxyl radical was formed, and the subsequent chemistry follows that of the photochemically generated radical. |
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| Item Description: | "Major subject: Chemistry." Vita. |
| Physical Description: | x, 168 leaves : illustrations ; 28 cm |
| Bibliography: | Includes bibliographical references (leaves 111-112). |