Full text loading...
No data available.
Please log in to see this content.
You have no subscription access to this content.
No metrics data to plot.
The attempt to load metrics for this article has failed.
The attempt to plot a graph for these metrics has failed.
The Absolute Configuration of Optically Active Molecules
1.L. Rosenfeld, Z. Physik 52, 161 (1928);
1.M. Born and P. Jordan, Elementare Quantenmechanik (Verlag. Julius Springer, Berlin, 1930), p. 250.
2.J. G. Kirkwood, J. Chem. Phys. 5, 479 (1937). The signs of the right sides of Eqs. (16), (19), (21), (24), (29), (33), and (35) of this article are in error and have been corrected in Sec. II of the present article.
3.E. U. Condon, Revs. Modern Phys. 9, 432 (1937);
3.Kauzmann, Walter, and Eyring, Chem. Revs. 26, 339 (1940).
4.This result is consistent with that obtained recently by x‐ray diffraction utilizing the phase shift near an absorption edge: Peerdeman, Van Bommel, and Bijvoet, Proc. Koninkl. Nederland. Akad. Wetenschap. 54B, 16 (1951).
5.We do not intend to imply by our terminology that the methylring interaction must contribute only a single term to It is more correct and in keeping with the intent of the theory to consider it as being itself the sum of three terms describing the interactions of the methyl group with the two carbons and oxygen of the ring, plus terms describing the interactions of the ring atoms with each other. (The sum of these latter terms describing interactions within the ring is probably small since the ring has a plane of symmetry in the absence of perturbing influences.) Thus the “methyl‐ring interaction term” actually comprises a sum of terms and the terminology is adopted for the sake of convenience; the optical properties of carbon and oxygen in such an environment are not sufficiently well known to allow separate calculation of these terms.
6.L. O. Brockway and P. C. Cross, J. Am. Chem. Soc. 58, 2407 (1936);
6.L. O. Brockway and P. C. Cross, 59, 1147 (1937)., J. Am. Chem. Soc.
7.H. J. Lucas and H. K. Garner, J. Am. Chem. Soc. 70, 990 (1948);
7.P. A. Levene and A. Walti, J. Biol. Chem. 68, 415 (1926).
8.Dickey, Fickett, and Lucas, J. Am. Chem. Soc. (to be published).
9.W. W. Wood and V. Schomaker, J. Chem. Phys. (to be published).
10.R. A. Oriani and C. P. Smyth, J. Chem. Phys. 17, 1174 (1949).
11.Fickett, Gamer, and Lucas, J. Am. Chem. Soc. 73, 5063 (1951).
12.The effects of temperature and solvent on optical rotation have been considered previously; C. O. Beckman and K. Cohen, J. Chem. Phys. 4, 784 (1936);
12.Kauzmann, Walter, and Eyring, Chem. Revs. 26, 373 (1940);
12.H. J. Bernstein and E. E. Pedersen, J. Chem. Phys. 17, 885 (1949).
13.The rotations in Table V and VI are for approximately 2–5 percent solutions. Measurements at lower concentrations showed that the rotation was nearly independent of concentration in all of the solvents used. The values in Tables V and IV may therefore be taken as those at infinite dilution.
14.J. G. Kirkwood, J. Chem. Phys. 2, 351 (1934).
15.This can be shown by distinguishing three cases: (1) The isomers have optical rotations of the same sign, which is obviously the same as that of the over‐all rotation. The magnitude of the over‐all rotation will then either increase or decrease with increasing temperature depending on the relative magnitudes of the rotations of the two isomers. (2) The isomers have rotations of opposite sign, and the sign of the over‐all rotation is the same as that of the trans‐form. The over‐all rotation will then decrease with increasing temperature. (3) The isomers have rotations of opposite sign, and the sign of the over‐all rotation is the same as that of the skew‐form. The over‐all rotation will then increase with increasing temperature. If the actual effect is a decrease in the observed rotation with increasing temperature, this is consistent with (1) and (2), not with (3). Hence the signs of the over‐all rotation and that of the trans‐forms are the same. The argument is similar for the opposite temperature effect.
Article metrics loading...