Acid-Base Equilibria of Substituted Pyridines in Nitromethane

Abstract

In the framework of our studies on acid=nbase equilibria in systems comprisingsubstituted pyridines and nonaqueous solvents, acid dissociation constants havebeen determined potentiometrically for a variety of cationic acids conjugatedwith pyridine and its derivatives in the polar protophobic aprotic solvent nitromethane. The potentiometric method enabled a check as to whether and to whatextent cationic homoconjugation equilibria of the BH+/B type, as well as cationicheteroconjugation equilibria in BH+/B1 systems without proton transfer, are setup in nitromethane. The equilibrium constants were compared with thosedetermined in water and two other polar protophobic aprotic solvents, propylenecarbonate and acetonitrile. The pKa values of acids conjugate to the N-bases innitromethane fall in the pKa range of 5.84 to 17.67, i.e., 6 to 7 pKa units, onaverage, higher than in water, 1 to 2 units higher than in propylene carbonate,and less than 1 unit lower than in acetonitrile. This means that the basicity ofthe pyridine derivatives increases on going from propylene carbonate throughnitromethane to acetonitrile. Further, it was found that the sequence of the pKachanges of the protonated amines was consistent in all three media, thus providingthe basis for establishing linear correlations among these values. In the majorityof the BH+/B systems in nitromethane, cationic homoconjugation equilibria havebeen established. The cationic homoconjugation constants, log KBHB+, arerelatively low, falling in the range 1.60–2.89. A comparison of the homoconjugationconstants in nitromethane with those in propylene carbonate and acetonitrile showsthat nitromethane is a more favorable solvent for the cationic homoconjugationequilibria than the other two solvents. Moreover, results of the potentiometricmeasurements revealed that cationic heteroconjugation equilibria were not presentin the majority of the BH+/B1 systems in nitromethane. The heteroconjugationconstant could be determined in one system only, with logdiKBHB1+ = 2.56.