Basicities and structures of 4,4,6-trimethyl-2-arylamino-5,6-dihydro-4H-1,3-thiazines and 4,4,6-trimethyl-2-arylamino-5,6-dihydro-4H-1,3-oxazines

The relative basicities of 4,4,6-trimethyl-2-arylamino-5,6-dihydro-4H-1,3-thiazines and 4,4,6-trimethyl-2-arylamino-5, 6-dihydro-4H-1,3-oxazines, which are capable of amine-imine tautomerism, and of model compounds with fixed amine and imine structures were determined by potentiometric titration in methanol. Good correlation of the pK_avalues with the Hammett constants in the investigated reaction series was found. The inapplicability of the use of the pK_avalues of model compounds for the determination of the tautomeric equilibrium constants in the case of some N-heterocyclic amines of nonaromatic character with an aryl substituent attached to the exocyclic nitrogen atom of the amidine fragment of the molecule is demonstrated.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1621–1624, December, 1976.