Stereochemistry of HOH and HOAc elimination from 1-tetralol and 1-acetoxytetralin radical cations

摘要: Water and acetic acid eliminations from 1-tetralin radical cations have been shown previously to be highly regiospecific 1,4 processes. Utilizing deuterium labeling, high resolution peak ratio measurements metastable ion defocusing techniques, the stereochemistry of these processes has investigated. cis-4-d1- trans-4-d1-1-Tetralol both lose HOH DOH in appreciable amounts; similarly, acetoxy derivatives HOAc DOAc. These results are interpreted terms an ionic epimerization which operates competition with a stereospecific elimination mechanism. A hydrogen exchange process occurs between 4-carbon oxygen atom situated on 1-carbon 1-tetralol also observed. This accounts for observed H/D ratios ethene reaction various labeled 1-tetralols.