A series of ortho-substituted NIN1-dimethyl-N2-phenylformamidines (o-FDM P) have been synthesized and their structure determined by i.r. and 'H n.m.r. methods. All, except the hydroxy derivative, have the same structure ( E ) . In the case of the hydroxy derivative an intramolecular hydrogen bond appears, and thus two structures Z (20%) and E (80%) are observed in the 'H n.m.r. spectrum in CDCI,. The influence of the ortho-substituent on the retention indices, determined on a non-polar column, and on the pK, values, measured in 95.6% ethanol (azeotrope) and in water is discussed, and compared with those observed for meta-and para-derivatives. The retention indices of the ortho-derivatives, except the hydroxy derivative, obey the same linear correlation as meta-, para-, and other alkyl and aralkyl derivatives. A deviation of the pK, values of the ortho-derivatives from the linear correlations found for the meta-and para-derivatives are explained by steric effects of the substituent and medium effects.This paper reports the influence of ortho-substituents on the physicochemical properties of N ' N '-dimethyl-N ,-phenyl-