Cyclodimerization of crotonaldehyde to form cyclohexadienecarbaldehydes and tolaldehydes over solid base catalysts

The cyclodimerization of crotonaldehyde was performed over acid or base catalysts in the gas phase. We first attempted the reaction over various acid and base catalysts using a pulse reactor. The typical bases, CaO and MgO, effectively promoted the reaction to form methylcyclohexadienecarbaldehydes (MCHC) and tolaldehydes. In contrast, no significant formation of the dimers was observed over the acid catalysts, such as SiO2-Al2O3 and H-mordenite. Aluminum oxide also promoted the dimerization, indicating that the dimerization proceeds on the weaker base sites. The main products in the formed dimers were 6-methylcyclohexa-1,3-dienecarbaldehyde and o-tolualdehyde. In addition, small amounts of 4-methylcyclohexa-1,5-dienecarbaldehyde and p-tolaldehyde were produced as dimers. When the dimerization was performed over CaO, MgO, and Al2O3 using a fixed-bed flow reactor, the catalytic activities of all the catalysts significantly decreased during the initial stage of the reaction. The TG-DTA analysis of the used catalysts clearly indicated that a large amount of the condensation products had adsorbed on the catalyst surface. The maximum selectivity to the dimers (MCHC and tolaldehydes) was 38% for an approximate 30% conversion, which was obtained during the initial stage of the reaction over the Al2O3 and CaO catalysts.