Amazing reaction medium: Supercritical carbon dioxide, with zero dipole moment, lower dielectric constant than pentane, and non‐hydrogen‐bonding behavior, ionizes carbon–halogen bonds, dissociates the resulting ion pairs, and escapes from capture by the carbocation intermediates at temperatures above 40 °C. These properties allow the observation of carbocation chemistry in the absence of acids.

No solvent, no reaction: ethanol inhibits SN1 reactions of alkyl halides in scCO2 by competing with the substrate for solvation.

scCO2, a non-polar solvent with a dielectric constant lower than n-pentane, promotes the electrophilic bromination of aromatics as efficiently as strongly ionizing solvents such as aqueous acetic and trifluoroacetic acids.

No abstract