The reactivity of o-hydroxybenzyl alcohol and derivatives in solution at elevated temperatures

The reactivity of o-hydroxybenzyl alcohol (o-HBA, 1), as a model compound f or lignin, has been studied in various solvents between 390 and 560 K. Both in polar and apolar solvents the benzylic cation is the reactive intermedi ate. In alcoholic solvents, the benzylic cation reacts with the solvent to give the corresponding ethers. Relative reaction rates have been determined for different alcohols; a factor of 14 is encountered between the most (me thanol) and least (tert-butyl alcohol) reactive ones. The etherification is reversible, in contrast to the electrophilic aromatic substitution with ph enol and anisole, for which k(PhOH) = 1 x 10(5) M-1 s(-1) and k(anisole) = 1 x 10(4) M-1 s(-1), at 424 K. In apolar hydroaromatic solvents, 7H-benz[de ]anthracene, 9,10-dihydroanthracene, and 9,10-dihydrophenanthrene, the form ation of o-cresol proceeds via hydride transfer from the solvent to the ben zylic cation; rate constants at 555 K are 2 x 10(6), 5 x 10(4), and 5 x 10( 3) M-1 s(-1), respectively.