Methanol, higher alcohols and ethers are synthesized on a large scale
over heterogeneous catalysts with specific functionalities. When coppe
r is the key component of the methanol and higher alcohol catalysts, a
lkali promotion gives rise to dramatic enhancements of yields due to n
on-dissociative activation of CO and promotion of aldol coupling with
reversal of oxygen retention. Ethers are formed from alcohols over sol
id acid catalysts, both organic sulfonic resins and inorganic compound
s such as zeolites, by a preferential surface S(N)2 pathway. This is e
xemplified by O-18 retention in reactions of two different alcohols, c
hirality inversion where asymmetric carbon is involved, and kinetics t
hat reflect competition of the reactant alcohols for surface acid site
s. Transition state shape selectivity is exemplified in the reaction o
f 2-pentanol and ethanol in H-ZSM-5 and selectivity due to orthogonali
ty of the S(N)2 pathway to main channel direction in the formation of
dimethyl ether in H-mordenite.