Kinetic Trapping of an Out-of-Equilibrium Dynamic Library of Imines by Changing Solvent

A well-behaved dynamic library composed of two imines and corresponding amines was subjected to the action of an activated carboxylic acid (ACA), whose decarboxylation is known to be base promoted, in different solvents, namely CD2Cl2, CD3CN, and mixtures of them. Two non-equilibrium systems are consequently obtained: i) a dissipative (CD2Cl2) and ii) an out-of-equilibrium (CD3CN) dynamic library whose composition goes back to equilibrium after a given time. In the former case, the library is fully coupled with the decarboxylation of the ACA, while in the latter, an energy ratchet operates. In the mixed solvents, the library exhibits a mediated behavior. Interestingly, in the presence of an excess of added ACA, the different behavior of the imine library in the two solvents is expected to manifest only when the excess acid is consumed. When an Activated Carboxylic Acid (ACA) is employed to perturb a dynamic library of imines, the nature of the solvent has a crucial role in defining the non-equilibrium state of such library. A dissipative dynamic library in CD2Cl2, fully coupled with the decarboxylation of the ACA, or a kinetically trapped out-of-equilibrium dynamic library in CD3CN can be generated. image