Alumina: Catalyst and support. XL (1) ring expansion during the dehydration of alcohols over alumina catalysts (2)

Article abstract of DOI:10.1016/0021-9517(71)90008-X

An investigation of ring expansion during the alumina-catalyzed dehydration of alcohols was made by the micro-pulse technique. The dehydration at 380 °C over fresh alumina of cyclobutane-, cyclopentane-, cyclohexane-, and cycloheptane-methanol yielded 99, 55, 7, and 6% of ring-expanded product, respectively, whereas over alumina which has been deactivated by passing large quantities of alcohol over it, 100, 74, 19, and 18% of the ring-expanded products were found. The stereochemical aspects of this catalytic reaction were investigated by the dehydration of cis- and trans-4-t-butylcyclohexanemethanol. More ring expansion and a higher conversion to olefins occurred in the dehydration of the cis alcohol than of the trans alcohol. In the dehydration of 1-methyl-1-cyclohexanemethanol at 310 °C, 60% of product formation involved methyl migration whereas 40% involved ring expansion. The percentage of ring expansion increased to 55 when deactivated catalyst was used. More skeletal rearrangement was found in dehydrations over alumina which had been deactivated by passing either an unsaturated or a saturated hydrocarbon over it than when fresh catalyst was used. Although the presence of sodium ions or pyridine on the catalyst lowered the amount of double bond isomerization which occurred, it did not affect the amount of skeletal rearrangement or the deactivation of the catalyst. The dehydration of 2-methylpropanol over alumina catalyst was reinvestigated and it was found that the extent of skeletal isomerization to produce n-butenes increases with the deactivation of the aluminas.