Van't Hoff's “Stereochemistry”

Abstract

THE review of the above by “F. R. J.” in NATURE, p. 436, raises some important points in connection with this peculiarly fascinating branch of chemical science. In referring to the recent ingenious and attractive theory of P. A. Guye, that the numerical value of optical activity is dependent upon the relative masses of the four groups attached to the asymmetric carbon atom, and which carries with it the corollary that if two of these four groups are of equal mass the rotatory power will cease, your reviewer states that Guye “was unable to verify this view in all strictness.” I think, however, that he hardly emphasisės sufficiently that this important corollary has in every ease, when put to the test of direct experiment, broken down. As far as I am aware, there is not a single instance of an asymmetric carbon atom attached to four groups qualitatively distinct, being found optically inactive in consequence of two of those groups being quantitatively equal in mass. Indeed some such substances are not merely active but powerfully so. The reviewer considers that this inadequacy of Guye's theory is palliated by the alleged fact that the amount of rotatory power of the esters of an active acid is determined by the weight of the alkyl-group. This point, which is one of the cardinal pillars of Guye's theory, I have recently put to the test of actual experiment, by measuring the rotatory power of a number of the esters of active glyceric acid, which have been prepared by Mr. J. MacGregor and myself. In this investigation we found the most extraordinary verification of Guye's theory, as far as the optical properties of the normal series of methyl, ethyl, and propyl glycerates were concerned; with the appearance of isomerism, however, this regularity ceases, thus the isopropyl glycerate has markedly lower rotation than the normal one, whilst the normal and secondary butyl compounds have a lower rotation than the isobutyl ester. Nor are these differences consistently explicable by taking into consideration the interatomic distances, as measured by atomic volume, for the molecular volume of the normal propyl glycerate with its greater rotation is less than that of the isopropyl compound with its smaller rotation, whilst the molecular volumes of the isobutyl and secondary butyl glycerates are almost exactly equal, although the rotation of the former is much greater than that of the latter.