Skip to main content

Conformational Analysis

The Elevation of Two-Dimensional Formulas into the Third Dimension

  • Chapter
  • 214 Accesses

Abstract

The subject of this essay concerns the progression from two-dimensional to three-dimensional structural formulas, with emphasis on the development of conformational analysis. We are all aware that the second half of the 20th century has been a golden age in the development of stereochemistry, from Barton’s conformational analysis in 1950, through the Woodward-Hoffmann rules and Woodward’s ingenious diastereoselective syntheses, to the many highly efficient enantioselective syntheses of today. Less well known — at least to those not schooled in the history of chemistry — is the fact that an at least equally brilliant development in structural chemistry occurred 100 years earlier, specifically in the years 1858 to 1892.

The erratum of this chapter is available at http://dx.doi.org/10.1007/978-1-4899-0268-9_35

This is a preview of subscription content, log in via an institution.

Buying options

Chapter
USD   29.95
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
eBook
USD   129.00
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
Softcover Book
USD   169.99
Price excludes VAT (USA)
  • Compact, lightweight edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info
Hardcover Book
USD   169.99
Price excludes VAT (USA)
  • Durable hardcover edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info

Tax calculation will be finalised at checkout

Purchases are for personal use only

Learn about institutional subscriptions

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References and Notes

  1. a) cf. O. T. Benfey, ed., Classics in the Theory of Chemical Combination, Krieger, Malabar, FL, 1981, pp. 1-108.

    Google Scholar 

  2. b) id., From Vital Force to Structural Formulas, Houghton Mifflin, Boston, MA, 1964, pp. 1-75.

    Google Scholar 

  3. The term “constitution” was used prior to 1858, if perhaps vaguely. In the title of Loschmidt’s 1861 booklet (ref. 8) it includes connectivity and it is in this latter sense that the term has been defined in a recent text: E. L. Eliel, S. H. Wilen, Stereochemistry of Organic Compounds, Wiley, 1994. In the same text “structure” is defined as the complete three-dimensional array of the atoms in a molecule: Structure = Constitution + Configuration + Conformation. Butlerov (ref. 17) in his original definition of structure calls it the manner of the mutual linkage of atoms in a chemical compound, and while in 1861 this may have been synonymous with constitution, in modern parlance the “manner of mutual linkage” may be considered to include the three-dimensional array, i.e. configuration and conformation.

    Google Scholar 

  4. A. S. Couper, C. R. Acad. Sci. 46, 1157 (1858).

    Google Scholar 

  5. A. S. Couper, C. R. London, Edinburgh, Dublin Philos. Mag. J. Sci. [4] 16, 104 (1858).

    Google Scholar 

  6. A. S. Couper, C. R. London, Ann. Chim. (Paris) [3] 53, 489 (1858); see also ref. la, pp. 132 and 136.

    Google Scholar 

  7. A. Kekulé, Liebigs Ann. Chem. Pharm. 106, 129 (1858); translated in ref. la, p. 109.

    Article  Google Scholar 

  8. cf. R. Anschütz, August Kekulé, Verlag Chemie, Berlin, 1929, Vol. I, pp. 156, 157. Kekulé’s “caterpillar” formulas were apparently presented in his lectures as early as 1857: ibid., p. 162.

    Google Scholar 

  9. A. Kekulé, Lehrbuch der Organischen Chemie, Enke, Erlangen, Vol. 1, 1861.

    Google Scholar 

  10. Polemics were the order of the day in the 1860’s. Kekulé complained about Couper’s publication in Compt. rend.: A. Kekulé, C. R. Acad. Sci. 47, 378 (1858) and, in a letter to Erlenmeyer in 1862 (ref. 5, p. 305), calls Loschmidt’s Konstitutionsformeln (constitutional formulas) “Confusionsformeln” (confused formulas). However, Kekulé himself got confused on at least one occasion (ref. 5, pp. 290, 291): he gives two different formulas for propanol-2: which he considers isomeric; in fact, of course, they are only different manners of writing the same constitutional formula.

    Google Scholar 

  11. J. Loschmidt, Konstitutionsformeln der organischen Chemie in graphischer Darstellung, R. Anschütz, ed., Ostwald’s Klassiker No 190, Engelmann, Leipzig, 1913. The original appeared in 1861 under the title “Chemische Studien”; the Anschütz edition available to the author contains some improvements in the original formula drawings.

    Google Scholar 

  12. Ref. 6, footnote on p. 160.

    Google Scholar 

  13. Ref. 8, Scheme 185.

    Google Scholar 

  14. W. J. Wiswesser, Aldrichimica Acta 22, 17 (1989).

    CAS  Google Scholar 

  15. cf. G. P. Schiemenz, Sudhoffs Arch. 78 (1), 41 (1994).

    Google Scholar 

  16. A. Kekulé, Bull. Soc. Chim. Fr. Nouvelle sen [3] 1, 98 (1865).

    Google Scholar 

  17. A. Kekulé, Bull. Acad. R. Belg. [2] 19, 551 (1865).

    Google Scholar 

  18. A. Kekulé, Justus Liebigs Ann. Chem. 137, 129 (1866). See also.

    Article  Google Scholar 

  19. A. Kekulé, Ber. Dtsch. Chem. Ges. 2, 362 (1869).

    Article  Google Scholar 

  20. A. Kekulé, Justus Liebigs Ann. Chem. 162, 77 (1872).

    Article  Google Scholar 

  21. A. Kekulé, Lehrbuch der Organischen Chemie, Enke, Erlangen, Vol. 2, 1866, pp. 514, 515.

    Google Scholar 

  22. A. Crum Brown, Trans. R. Soc. Edinburgh 23, 707 (1864).

    Article  Google Scholar 

  23. A. Crum Brown, Trans. R. Soc. Edinburgh 24, 331 (1866).

    Article  Google Scholar 

  24. A. Crum Brown, J. Chem. Soc. 18, 230 (1865).

    Article  Google Scholar 

  25. A. Kekulé, Z. f. Chem. N. F. 3, 214 (1867); see especially p. 218. Reprinted in ref. 5, Vol. II, p. 525.

    Google Scholar 

  26. A. M. Butlerov, Z. Chem. Pharm., 4, 549 (1861); The journal abbreviation stands for “Zeitschrift für Chemie und Pharmacie”, a journal founded by Kekulé, Erlenmeyer and others at the University of Heidelberg in 1858 as “Kritische Zeitschrift für Chemie, Physik und Mathematik”, renamed with Vol 3, 1860 as above and renamed again “Zeitschrift für Chemie” with Vol. 8, 1865. (I am indebted to O. T. Benfey for this information.) The journal seems to have disappeared in the 1870’s, after Ber. Dtsch. Chem. Ges. was founded in 1868. It seems that many of the early “structural chemists” published in this journal.

    Google Scholar 

  27. A. M. Butlerov, Z. Chem. Pharm. 5, 297 (1862).

    Google Scholar 

  28. A. M. Butlerov, Z. Chem. Pharm. 6, 500 (1863).

    Google Scholar 

  29. L. Pasteur, Recherches sur la Dissymétrie Moléculaire des Produits Organiques Naturels, two lectures delivered in Paris, January 20 and February 3, 1860. See J. Jacques, ed., Sur la Dissymétrie Moléculaire, Christian Bourgois, Paris, 1986. An English translation under the erroneous title “Researches on the Molecular Asymmetry of Natural Organic Products” may be found in G. M. Richardson, ed., The Foundations of Stereochemistry, American Book Co., New York, 1901, and in Alembic Club Reprint No. 14. (Asymmetry and Dissymmetry are not equivalent terms; see ref. 65, p. 1197.).

    Google Scholar 

  30. J. H. van’t Hoff, Arch. Ned. Sci. Exactes Nat. 9, 445 (1874).

    Google Scholar 

  31. J. H. van’t Hoff, Bull Soc. Chim. Fr. [2], 23, 295 (1875). The original version was published in Dutch in a pamphlet in 1874. For an English translation, see ref. 1 a, p. 151.

    Google Scholar 

  32. J. A. Le Bel, Bull. Soc. Chim. Fr. [2], 22, 337 (1874); translated in ref. la, p. 161.

    Google Scholar 

  33. e.g. S. F. Mason. Top. Stereochem. 9, 1 (1976).

    Article  CAS  Google Scholar 

  34. H. A. M. Snelders, in “van’t Hoff-Le Bel Centennial”, O. B. Ramsey, ed., Am. Chem. Soc, Washington, DC (Symposium Series No. 12), 1975, p. 66.

    Google Scholar 

  35. J. H. van’t Hoff, La Chimie dans l’Espace, Bazendijk, Rotterdam, 1875, pp. 13-14.

    Google Scholar 

  36. H. Kolbe, J. Prakt. Chem. [2] 15, 473 (1877).

    Google Scholar 

  37. cf. P. H. Hermans, in “van’t Hoff-Le Bel Centennial”, O. B. Ramsey, ed., Am. Chem. Soc, Washington, DC, 1975, p. 123.

    Google Scholar 

  38. C. A. Bischoff, Ber. Dtsch. Chem. Ges. 23, 620 (1890). cf. G. V. Bykov, ref. 26, p. 114.

    Article  Google Scholar 

  39. A. Baeyer, Ber. Dtsch. Chem. Ges. 18, 2269 (1885).

    Article  Google Scholar 

  40. A. Baeyer, Justus Liebigs Ann. Chem. 258, 145 (1890).

    Article  Google Scholar 

  41. H. Sachse, Ber. Dtsch. Chem. Ges. 23, 1363 (1890).

    Article  Google Scholar 

  42. H. Sachse, Z. Phys. Chem. 10, 203 (1892).

    Google Scholar 

  43. O. Aschan, Justus Liebigs Ann. Chem. 271, 262 (1892).

    Article  Google Scholar 

  44. A. Werner, H. E. Conrad, Ber. Dtsch. Chem. Ges. 32, 3046 (1899).

    Article  CAS  Google Scholar 

  45. O. Aschan, Chemie der Alicyklischen Verbindungen, Vieweg, Braunschweig, 1905.

    Google Scholar 

  46. E. W. M. Mohr, Chem. Zentralbl. 1915 II, 1065 (Sitzungsber. Heidelberg. Akad. Wiss., Math. Naturwiss. Kl., Abt. A, 1915, 7. Abh.).

    Google Scholar 

  47. E. W. M. Mohr, J. Prakt. Chem. [2] 98, 315 (1918).

    Article  Google Scholar 

  48. E. W. M. Mohr, J. Prakt. Chem. 103, 316 (1922).

    Article  CAS  Google Scholar 

  49. W. Hückel, Justus Liebigs Ann. Chem. 441, 1 (1925).

    Article  Google Scholar 

  50. J. Boëseken, H. G. Derx, Reel. Trav. Chim. Pays-Bas 40, 519, 529 (1921).

    Article  Google Scholar 

  51. J. Boëseken, Recl. Trav. Chim. Pays-Bas 40, 553 (1921).

    Article  Google Scholar 

  52. P. H. Hermans, Z. Phys. Chem. 113, 337 (1924).

    Google Scholar 

  53. S. Winstein, N. J. Holness, J. Am. Chem. Soc. 77, 5562 (1955).

    Article  CAS  Google Scholar 

  54. S. B. Hendricks, C. Biticke, J. Am. Chem. Soc. 48, 3007 (1926).

    Article  CAS  Google Scholar 

  55. R. G. Dickinson, C. Bilicke, J. Am. Chem. Soc. 50, 764 (1928).

    Article  CAS  Google Scholar 

  56. R. S. Rasmussen, J. Chem. Phys. 11, 249 (1943).

    Article  CAS  Google Scholar 

  57. K. W. F. Kohlrausch, H. Wittek, Z. Phys. Chem. 48B, 177 (1941).

    Google Scholar 

  58. cf. O. Hassel, H. Viervoll, Acta Chem. Scand. 1, 149 (1947).

    Article  CAS  Google Scholar 

  59. J. G. Aston, S. C. Schumann, H. L. Fink, P. M. Doty, J. Am. Chem. Soc. 63, 2029 (1941).

    Article  CAS  Google Scholar 

  60. R. L. Shriner, R. Adams, C. Marvel, “Stereochemistry” in H. Gilman, ed., Organic Chemistry, 2nd ed., Vol. 1, Wiley, New York, 1943, p. 321.

    Google Scholar 

  61. J. D. Kemp, K. S. Pitzer, J. Chem. Phys. 4, 749 (1936).

    Article  CAS  Google Scholar 

  62. J. D. Kemp, K. S. Pitzer, J. Am. Chem. Soc. 59, 276 (1937).

    Article  CAS  Google Scholar 

  63. K. S. Pitzer, J. Chem. Phys. 5, 473 (1937).

    Article  CAS  Google Scholar 

  64. cf. S. Mizushima, Structure of Molecules and Internal Rotation, Academic Press, New York, 1954.

    Google Scholar 

  65. S. Mizushima, Pure Appl. Chem. 7, 1 (1963).

    Article  CAS  Google Scholar 

  66. O. Hassel, Tidsskr. Kjemi Bergves. Metall. 3 [5], 32 (1943); transi, by.

    CAS  Google Scholar 

  67. K. Hedberg, Top. Stereochem. 6, 11 (1971).

    Google Scholar 

  68. C. W. Beckett, K. S. Pitzer, R. Spitzer, J. Am. Chem. Soc. 69, 2488 (1947);cf.

    Article  CAS  Google Scholar 

  69. E. J. Prosen, W. H. Johnson, F. D. Rossini, J. Res. Natl. Bur. Stand. 39, 173 (1947).

    Article  CAS  Google Scholar 

  70. J. E. Leonard, G. S. Hammond, H. E. Simmons, J. Am. Chem. Soc. 97, 5052 (1975).

    Article  CAS  Google Scholar 

  71. D. H. R. Barton, Experientia 6, 316 (1950).

    Article  CAS  Google Scholar 

  72. D. H. R. Barton, reprinted in Top. Stereochem. 6, 1 (1971).

    Article  Google Scholar 

  73. E. L. Eliel, 100+ Years of Conformational Analysis, chapter 1 in ref. 69, p. 1.

    Google Scholar 

  74. See also D. H. R. Barton, Some Recollections of Gap Jumping, American Chemical Society, Washington, DC, 1991.

    Google Scholar 

  75. E. L. Eliel, From Cologne to Chapell Hill, American Chemical Society, Washington, DC, 1990.

    Google Scholar 

  76. E. L. Eliel, Experientia 9, 91 (1953).

    Article  CAS  Google Scholar 

  77. J. Read, W. J. Grubb, J. Chem. Soc. 1934, 1779.

    Google Scholar 

  78. E. L. Eliel, R. S. Ro, Chem. Ind. (London) 1956, 251.

    Google Scholar 

  79. cf. C. H. Bushweller, Stereodynamics of Cyclohexane and Substituted Cyclohexanes. Substituent A Values, chapter 2 in ref. 69, p. 25.

    Google Scholar 

  80. E. L. Eliel, C. A. Lukach, J. Am. Chem. Soc. 79, 5986 (1957).

    Article  CAS  Google Scholar 

  81. E. L. Eliel, R. S. Ro, J. Am. Chem. Soc. 79, 5992 (1957).

    Article  CAS  Google Scholar 

  82. E. L. Eliel, Chem. Ind. (London) 1959, 568.

    Google Scholar 

  83. F. R. Jensen, D. S. Noyce, C. H. Sederholm, A. J. Berlin, J. Am. Chem. Soc. 82, 1256 (1960).

    Article  CAS  Google Scholar 

  84. F. R. Jensen, D. S. Noyce, C. H. Sederholm, A. J. Berlin, J. Am. Chem. Soc. 84, 386 (1962).

    Article  CAS  Google Scholar 

  85. E. L. Eliel, S. H. Wilen, Stereochemistry of Organic Compounds, Wiley, New York, 1994, chapter 11.

    Google Scholar 

  86. R. L. Wilier, E. L. Eliel, J. Am. Chem. Soc. 99, 1925 (1977).

    Article  Google Scholar 

  87. E. L. Eliel, D. Kandasamy, C.-Y. Yen, K. D. Hargarve, J. Am. Chem. Soc. 102, 3698 (1980).

    Article  CAS  Google Scholar 

  88. E. L. Eliel, K. D. Hargrave, K. M. Pietrusiewicz, M. Manoharan, J. Am. Chem. Soc. 104, 3635 (1982). See also ref. 54, p. 8.

    Article  CAS  Google Scholar 

  89. cf. E. L. Eliel, M. C. Knoeber, J. Am. Chem. Soc. 88, 5347 (1966).

    Article  CAS  Google Scholar 

  90. cf. E. L. Eliel, M. C. Knoeber, J. Am. Chem. Soc. 90, 3444 (1968).

    Article  CAS  Google Scholar 

  91. E. L. Eliel, N. L. Allinger, S. J. Angyal, G. A. Morrison, Conformational Analysis, Interscience-Wiley, New York, 1965; reprinted by Am. Chem. Soc, Washington, DC, 1981.

    Google Scholar 

  92. E. Juaristi, ed., Conformational Behavior of Six-membered Rings, VCH, New York, 1995.

    Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Editor information

Editors and Affiliations

Rights and permissions

Reprints and permissions

Copyright information

© 1997 Springer Science+Business Media New York

About this chapter

Cite this chapter

Eliel, E.L. (1997). Conformational Analysis. In: Fleischhacker, W., Schönfeld, T. (eds) Pioneering Ideas for the Physical and Chemical Sciences. Springer, Boston, MA. https://doi.org/10.1007/978-1-4899-0268-9_3

Download citation

  • DOI: https://doi.org/10.1007/978-1-4899-0268-9_3

  • Publisher Name: Springer, Boston, MA

  • Print ISBN: 978-1-4899-0270-2

  • Online ISBN: 978-1-4899-0268-9

  • eBook Packages: Springer Book Archive

Publish with us

Policies and ethics