Hydration equilibria of 9-acridinecarboxaldehyde

Abstract

Hydration rate constants and equilibrium constants have been obtained for 9-acridinecarboxaldehyde in aqueous solution. Under acidic conditions where the acridine is protonated, signals for the hydrate and free aldehyde forms can be observed as separate species in the 1H NMR spectrum. Integration provides the hydration equilibrium constant[Formula: see text] Using an apparent acidity constant obtained from a spectroscopic titration curve, the rate–pH profile was fitted to provide the hydration constant for the equilibration of the neutral acridines, KH = 0.07. This analysis also provides the acidity constants for the two acridinium ions, the aldehyde with pK = 3.78 and the hydrate with pK = 5.36. A comparison with the 4-pyridinecarboxaldehdye system reveals that the [Formula: see text] ratios for the acridine and pyridine are the same within experimental error, but that the acridine and acridinium aldehydes are 20-fold less hydrated than their pyridine analogs. A comparison with benzaldehydes reveals that, in their reactivities, the two heterocyclic aldehydes behave in a similar manner. Thus, for example, plots of log kH for the acid-catalyzed dehydration and hydrations versus log Kh for the equilibrium hydration show single correlation lines including the points for the benzaldehydes and heterocyclic aldehydes (but not the aliphatic aldehydes).