Abstract

This paper is a survey of the application of plane polarized light to the determination of the configuration of asymmetric organic compounds. The concept of asymmetric structures is discussed and the methods of separation of optical isomers have been indicated. Spectropolarimeters for the determination of rotatory dispersion curves are described and examples of normal and anomalous rotatory dispersion curves are given.

© 1951 Optical Society of America

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References

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  1. (a)General reference in stereochemistry and optical activity: Shriner, Adams, and Marvel, “Stereochemistry,” in H. Gilman’s Organic Chemistry (John Wiley and Sons, New York, 1943), second edition, Vol. 1, pp. 214–487. (b)G. W. Wheland, Advanced Organic Chemistry (John Wiley and Sons, New York, 1949), second edition. (c)W. Heller, “Polarimetry,” in A. Weissberger’s, Physical Methods of Organic Chemistry (Interscience Publishers, New York, 1949), second edition, Vol. 1, Part 2, pp. 1491–1610. (d)K. Freudenberg, Stereochemie (Deutick, 1933) (Edwards Bros., Ann Arbor, Michigan, 1945).
  2. W. R. Brode and C. H. Jones, J. Opt. Soc. Am. 31, 743 (1941).
    [Crossref]
  3. E. E. Pickett and W. R. Brode (from unpublished material submitted for the Ph.D. degree at the Ohio State University by E. E. Pickett under the direction of W. R. Brode). Reported in abstract form in Abstracts of Doctoral Dissertations, The Ohio State University Press56, 343 (1949).
  4. C. S. Hudson, J. Am. Chem. Soc. 40, 813 (1918).
    [Crossref]

1941 (1)

1918 (1)

C. S. Hudson, J. Am. Chem. Soc. 40, 813 (1918).
[Crossref]

Adams,

(a)General reference in stereochemistry and optical activity: Shriner, Adams, and Marvel, “Stereochemistry,” in H. Gilman’s Organic Chemistry (John Wiley and Sons, New York, 1943), second edition, Vol. 1, pp. 214–487. (b)G. W. Wheland, Advanced Organic Chemistry (John Wiley and Sons, New York, 1949), second edition. (c)W. Heller, “Polarimetry,” in A. Weissberger’s, Physical Methods of Organic Chemistry (Interscience Publishers, New York, 1949), second edition, Vol. 1, Part 2, pp. 1491–1610. (d)K. Freudenberg, Stereochemie (Deutick, 1933) (Edwards Bros., Ann Arbor, Michigan, 1945).

Brode, W. R.

W. R. Brode and C. H. Jones, J. Opt. Soc. Am. 31, 743 (1941).
[Crossref]

E. E. Pickett and W. R. Brode (from unpublished material submitted for the Ph.D. degree at the Ohio State University by E. E. Pickett under the direction of W. R. Brode). Reported in abstract form in Abstracts of Doctoral Dissertations, The Ohio State University Press56, 343 (1949).

Gilman, H.

(a)General reference in stereochemistry and optical activity: Shriner, Adams, and Marvel, “Stereochemistry,” in H. Gilman’s Organic Chemistry (John Wiley and Sons, New York, 1943), second edition, Vol. 1, pp. 214–487. (b)G. W. Wheland, Advanced Organic Chemistry (John Wiley and Sons, New York, 1949), second edition. (c)W. Heller, “Polarimetry,” in A. Weissberger’s, Physical Methods of Organic Chemistry (Interscience Publishers, New York, 1949), second edition, Vol. 1, Part 2, pp. 1491–1610. (d)K. Freudenberg, Stereochemie (Deutick, 1933) (Edwards Bros., Ann Arbor, Michigan, 1945).

Hudson, C. S.

C. S. Hudson, J. Am. Chem. Soc. 40, 813 (1918).
[Crossref]

Jones, C. H.

Marvel,

(a)General reference in stereochemistry and optical activity: Shriner, Adams, and Marvel, “Stereochemistry,” in H. Gilman’s Organic Chemistry (John Wiley and Sons, New York, 1943), second edition, Vol. 1, pp. 214–487. (b)G. W. Wheland, Advanced Organic Chemistry (John Wiley and Sons, New York, 1949), second edition. (c)W. Heller, “Polarimetry,” in A. Weissberger’s, Physical Methods of Organic Chemistry (Interscience Publishers, New York, 1949), second edition, Vol. 1, Part 2, pp. 1491–1610. (d)K. Freudenberg, Stereochemie (Deutick, 1933) (Edwards Bros., Ann Arbor, Michigan, 1945).

Pickett, E. E.

E. E. Pickett and W. R. Brode (from unpublished material submitted for the Ph.D. degree at the Ohio State University by E. E. Pickett under the direction of W. R. Brode). Reported in abstract form in Abstracts of Doctoral Dissertations, The Ohio State University Press56, 343 (1949).

Shriner,

(a)General reference in stereochemistry and optical activity: Shriner, Adams, and Marvel, “Stereochemistry,” in H. Gilman’s Organic Chemistry (John Wiley and Sons, New York, 1943), second edition, Vol. 1, pp. 214–487. (b)G. W. Wheland, Advanced Organic Chemistry (John Wiley and Sons, New York, 1949), second edition. (c)W. Heller, “Polarimetry,” in A. Weissberger’s, Physical Methods of Organic Chemistry (Interscience Publishers, New York, 1949), second edition, Vol. 1, Part 2, pp. 1491–1610. (d)K. Freudenberg, Stereochemie (Deutick, 1933) (Edwards Bros., Ann Arbor, Michigan, 1945).

J. Am. Chem. Soc. (1)

C. S. Hudson, J. Am. Chem. Soc. 40, 813 (1918).
[Crossref]

J. Opt. Soc. Am. (1)

Other (2)

E. E. Pickett and W. R. Brode (from unpublished material submitted for the Ph.D. degree at the Ohio State University by E. E. Pickett under the direction of W. R. Brode). Reported in abstract form in Abstracts of Doctoral Dissertations, The Ohio State University Press56, 343 (1949).

(a)General reference in stereochemistry and optical activity: Shriner, Adams, and Marvel, “Stereochemistry,” in H. Gilman’s Organic Chemistry (John Wiley and Sons, New York, 1943), second edition, Vol. 1, pp. 214–487. (b)G. W. Wheland, Advanced Organic Chemistry (John Wiley and Sons, New York, 1949), second edition. (c)W. Heller, “Polarimetry,” in A. Weissberger’s, Physical Methods of Organic Chemistry (Interscience Publishers, New York, 1949), second edition, Vol. 1, Part 2, pp. 1491–1610. (d)K. Freudenberg, Stereochemie (Deutick, 1933) (Edwards Bros., Ann Arbor, Michigan, 1945).

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Figures (20)

Fig. 1
Fig. 1

Space models (above) and projection formulas (below) of dextro (d) and levo (l) optical isomers. (Note: molecular models are recommended for students interested in the construction and study of space isomers. A student set for this purpose is available from E. H. Sargent and Company of Chicago. [W. R. Brode and C. E. Boord, J. Chem. Ed. 9, 1774 (1932).]

Fig. 2
Fig. 2

Mechanical, biochemical, and chemical methods of resolution as devised by Pasteur (1860).

Fig. 3
Fig. 3

Mixed melting point diagrams of active isomers when added to racemic mixtures and racemic compounds.

Fig. 4
Fig. 4

Chemical resolution. The less soluble form (indicated by an underline) will crystallize as a pure compound when the solution is concentrated by evaporation or when the solubility is lowered by cooling. It should be noted that the two salts formed in the first reaction above are not antipodes but are diastereoisomers which have different physical properties (solubility). The antipodes or enantiomorphs of each of the salts formed in the first reaction are indicated in the center formulas.

Fig. 5
Fig. 5

Chemical resolution. (Upper reaction) The more soluble form is always contaminated by a small amount (l/n) of the less soluble form, the amount being dependent on the relative solubilities of the two forms. (Lower reaction) Incomplete or partial resolution where the less soluble form is a triple or mixed salt which crystallizes as a pure compound but yields only a partially resolved base on hydrolysis of the salt. The hydrolysis of the residue after removal of the crystalline solid yields a purer active base (of the opposite sign) than that obtained from the crystalline less soluble salt. [W. R. Brode and I. J. Wernert, J. Am. Chem. Soc. 55, 1685 (1933).]

Fig. 6
Fig. 6

Racemization. (Upper) Mechanical racemization by vibration or compression through a planar structure. (Lower) Chemical racemization through an inactive intermediate.

Fig. 7
Fig. 7

Space and projection formulas of dextro (d), levo (l), racemic (dl), and meso (i) tartaric acids. (M– – – M indicates a plane of symmetry in the meso form.)

Fig. 8
Fig. 8

Optical system of polarimeter in the Brode-Jones spectropolarimeter (reference 2). Rochon prism (adjustable polarizer), 3; single slit-diaphragm, 5; Wolaston prism (stationary analyzer), 6; rotating Rochon prism (beam alternator), 7; double slit-diaphragm, 11.

Fig. 9
Fig. 9

Optical system of Pickett-Brode spectropolarimeter (reference 3). Monochromator (Beckman), M; lenses, l1 and l2; polarizer (fixed), P; analyzer (adjustable), A; slit-diaphragms, D1 and D2 tube, S; photomultiplier tube in shielded housing at right.

Fig. 10
Fig. 10

Movable slit-diaphragm. B and D are the “bright” and “dark” images of the exit slit of the monochromator.

Fig. 11
Fig. 11

Anomalous rotatory dispersion as shown by optically active azo dyes, (formula indicated above). Rotatory dispersion curves are indicated for both d and l forms with calculated extension through absorption band. Absorption spectra of both enantiomorphic forms were identical. [W. R. Brode and R. Adams, J. Am. Chem. Soc. 46, 2032 (1924).]

Fig. 12
Fig. 12

Relation between optical rotation (B) and absorption (A) of levo dimethylamide of azidopropionic acid. Observed rotation curve (3) is resolvable into curves (4) and (5). Curve (5) is associated with the center of the absorption band (1) and is based on a modified Drude equation. [W. Kuhn and E. Braun, Naturwiss. 17, 227 (1929).]

Fig. 13
Fig. 13

Anomalous rotatory dispersion (1) and absorption spectrum (2) of aldehydo-d-ribose tetraacetate in chloroform. (See reference 3.)

Fig. 14
Fig. 14

Rotatory dispersion of sucrose. Continuous curve from Brode and Jones (reference 2), open circles from Pickett and Brode (reference 3), solid circles from Lowry and Richards [J. Chem. Soc. 125, 2511 (1924)].

Fig. 15
Fig. 15

Rotatory dispersion of d-chloronitrobutanol in chloroform at various concentrations. [J. F. Allen and W. R. Brode (from unpublished material submitted for the Ph.D. degree at the Ohio State University by J. F. Allen under the direction of W. R. Brode). Reported in abstract form in Abstracts of Doctoral Dissertations, The Ohio State University Press 54, 1 (1948).]

Fig. 16
Fig. 16

Normal rotatory dispersion of l-leucine and its sodium and hydrochloride salts. Conformity to a linear form in a reciprocal of rotation to wavelength squared relation. [J. W. Patterson and W. R. Brode, Arch. Biochem. 2, 247 (1943).]

Fig. 17
Fig. 17

Anomalous dispersion of certain α-amino acid salts. [J. W. Patterson and W. R. Brode, Arch. Biochem. 2, 247 (1943).]

Fig. 18
Fig. 18

Walden inversion [P. Walden, Ber. deut. chem. Ges. 26, 210 (1893)]. Inversion of configuration is postulated in those reactions with the circle below the center of the arrow.

Fig. 19
Fig. 19

Mechanism of addition of halogens (X2) to geometrical or planar isomers to produce optical isomers. (trans-addition implies addition of one X to each side of the carbon to carbon double bond by approach from opposite sides of the planar geometrical formula, cis-addition implies addition to the same side.)

Fig. 20
Fig. 20

Asymmetry of camphor. Space formula (above) projection formula (below).

Tables (2)

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Table I Physical properties of tartaric acids.

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Table II Determination of configuration.

Equations (4)

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d -Na ( NH 4 ) Tartrate + l -Na ( NH 4 ) r a c e m i c m i x t u r e Tartrate 27° C d l -Na ( NH 4 ) Tartrate r a c e m i c c o m p o u n d
2 d A + d l B d A d B + d A l B
α = A / λ 2 .
[ α ] = [ A 0 / ( λ 2 - λ 0 ) ] + [ A 1 / ( λ 2 - λ 1 ) ] + = [ A n / ( λ 2 - λ n ) ] .