An Investigation of the Preparation and Reactions of trans -3, 4-Dihydroxycyclohexyl Carbinol as a Cellulose Model Compound

The synthesis of the fully equatorial form of trans-3,4-dihydroxycyclohexyl carbinol was achieved and proof of its configuration is presented. The equatorial epimer was prepared from 3-cyclohexcne-1-carboxaldehyde which was oxidized to 3-cyclohexene-11-carboxylic acid, hydroxylated and esterified to give methyl trans-3,4-dihydroxycyclohexyl-1-carboxylate. This compound was converted to the fully equatorial configuration by the use of a base. Reduction of the epimeric ester yielded the desired model compound. Proof of stereochemistry of the model was obtained from infrared spectra, boiling and melting points, and gas chromatography. The boiling points of the epimers were in agreement with the von Auwers-Skita or Conformational Rule. The cellulose model compound was reacted in separate experiments with acetic anhydride, formic acid, and N-(methoxymethylol)acetamide. Gas chromatography was used to observe the rate of reaction and periodate oxidation to determine the amount of secondary hydroxyl reacted. The results indicated extensive participation of the secondary hydroxyls in all cases and correlated with the data reported for cellulose.