Mechanism and reactivity of the acyl chloride–alcohol system in the homogeneous phase and at the phase boundary

The present work is devoted to the search for energetically more favorable ways of the alcoholysis of acyl chlorides in a homogeneous medium and at the phase boundary. The implementation of an advantageous path is carried out by including a third molecule in the process: a reagent or a product. Aliphatic acyl chlorides are involved in the formation of termolecular hydrogen-bonded complexes, which leads to a decrease in reaction barriers and to the appearance of the probability of the reaction proceeding through the intermediate. In the alcoholysis of benzoyl chloride in a homogeneous medium, the addition of a third molecule does not speed up the reaction due to steric hindrances. A new principle of the action of a nonplanar adsorbent on the reaction system to control the reaction was proposed. In the force field of silica, the resulting hydrogen bonds and dispersion forces change the geometry of benzoyl chloride, which can significantly increase the efficiency of the process. The selectivity of the reaction is determined by the catalytic action of hydrogen bonds at the phase boundary. Separate stages of the process that affect the energy profile of the reaction have been established, which was not reported earlier.