Rotatory Power of optically active Benzoic Esters containing Ionisable ortho-substituents.

Abstract

Among the many and varied fields of present day chemistry, that of optical activity occupies a not unimportant position. The rotatory powers of the alkali and ammonium salts of d-sec-βoctyl hydrogen phthalate have been studied in alcoholic and aqueous solution. The rotations of the salts were found to be in the order H > Li > NH4 > Na > K > Rb. It has been concluded that the variation of the molecular rotation of the salts with concentration may be explained by assuming changes in the degree of dissociation of the electrolytes and a deforming influence of the cations on the optically active anions. The effect of the addition of inorganic salts of various valence types to 0.2 M aqueous solutions of d-sec-β-octyl sodium phthalate has been investigated. The series for the depressive influence of the alkali and ammonium chlorides on the rotatory power of the optically active electrolyte is Cs+> Rb+> K+> Na+> NH4+> Li+. The corresponding series for the divalent chlorides is Ba++> Sr++> Ca++> Mg++. It is concluded that the observed effects may be attributed mainly to a deforming influence of the positive ion on the optically active negative ion, the explanation involving a consideration of the ionic radii. It is worthy of comment that the above results have been obtained by use of a carboxylic acid containing no hydroxyl group.