Controlling the liberation rate of the in situ release of a chemical fuel for the operationally autonomous motions of molecular machines

Second-order rate constants of the aminolysis of 2-cyano-2-phenylpropanoic anhydride 3 by a series of N-methylanilines differently substituted in the aromatic moiety (4a-d) were measured in dichloromethane. The common reaction product of aminolysis is 2-cyano-2-phenylpropanoic acid 1, which is known to be an effective fuel for acid-base driven molecular machines, but cannot be used in molar excess with respect to the machine. The motivation behind the kinetic study has been the prospect of using the aminolysis of 3 to supply the machine with fuel at a rate that is never so high as to overfeed the system, thus avoiding the malfunction of the machine with concomitant waste of fuel. Knowledge of the kinetic parameters dictated the choice of 4c as the best nucleophile in the lot for feeding acid 1 into a catenane-based molecular machine at a rate that ensured a correct operation.