We report a new continuous method for forming ethers, acetals and ketals using solid acid catalysts,
DELOXAN ASP or AMBERLYST 15, and supercritical fluid solvents. In the case of ether formation, we
observe a high selectivity for linear alkyl ethers with little rearrangement to give branched ethers. Such
rearrangement is common in conventional syntheses. Our approach is effective for a range of n-alcohols up to
n-octanol and also for the secondary alcohol 2-propanol. In the reaction of phenol with an alkylating agent,
the continuous reaction can be tuned to give preferential O- or C-alkylation with up to 49% O-alkylation with
supercritical propene. We also investigate the synthesis of a range of cyclic ethers and show an improved
method for the synthesis of THF from 1,4-butandiol under very mild conditions.
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