Kinetic effects in water and ethylene glycol. Application to high pressure organic synthesis

Abstract

The kinetic effect of various Diels–Alder and Michael reactions is studied in water and ethylene glycol vs. organic solvents. The rate enhancement is considerable in water, much less in ethylene glycol. It is proposed that strong solvophobic interactions operate in water whereas the kinetic results in glycol are best explained by hydrogen bonding and polarity effects. From a synthetic point of view, use of the properties of water (hydrophobic interactions) or ethylene glycol (ionogenic medium) associated with the kinetic effect of high pressure may constitute an interesting multiactivation method to increase chemical reactivity. Examples of triactivation (high pressure catalytic Diels–Alder reactions in ethylene glycol) are given.