Deamination of 1-aminomethylcyclohexanol and solvolysis of (1- hydroxycyclohexyl) methyl P-toluenesulfonate

Abstract

The nitrous acid deamination of 1-aminomethylcyclohexanol was carried out in aqueous phosphoric acid medium. The products, identified by gas chromatography, were cycloheptanone, l-oxaspiro(2,5)octane, cyclohexanecarboxaldehyde, 1-hydroxymethylcyclohexanol and cyclohexanone along with three unidentified products. These were obtained in relative percentages of 1.2, 0.8, 81.1, 1.4 and 15.5, respectively. The product ratios were rationalized in terms of conformational equilibria in the intermediate diazonium cation.

The rates of solvolysis of (1-hydroxycyclohexyl)methyl p-toluenesulfonate were measured at 95°c and 35°c in a 50% ethanol-water mixture, and were found to be much greater than the solvolysis rates of 2-hydroxypropyl p-toluenesulfonate. These results are rationalized in terms of steric strain and the neighboring group effect. The products obtained by carrying out the solvolysis in pure water at 100°c were l-oxaspiro(2,5)octane, cyclohexanecarboxaldehyde and 1-hydroxymethylcyclohexanol. These were found in relative percentages of 22.3, 15.2, and 62.4, respectively. The differences in products and product ratios between the two reactions are discussed.