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.
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References and Notes
a) cf. O. T. Benfey, ed., Classics in the Theory of Chemical Combination, Krieger, Malabar, FL, 1981, pp. 1-108.
b) id., From Vital Force to Structural Formulas, Houghton Mifflin, Boston, MA, 1964, pp. 1-75.
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.
A. S. Couper, C. R. Acad. Sci. 46, 1157 (1858).
A. S. Couper, C. R. London, Edinburgh, Dublin Philos. Mag. J. Sci. [4] 16, 104 (1858).
A. S. Couper, C. R. London, Ann. Chim. (Paris) [3] 53, 489 (1858); see also ref. la, pp. 132 and 136.
A. Kekulé, Liebigs Ann. Chem. Pharm. 106, 129 (1858); translated in ref. la, p. 109.
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.
A. Kekulé, Lehrbuch der Organischen Chemie, Enke, Erlangen, Vol. 1, 1861.
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.
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.
Ref. 6, footnote on p. 160.
Ref. 8, Scheme 185.
W. J. Wiswesser, Aldrichimica Acta 22, 17 (1989).
cf. G. P. Schiemenz, Sudhoffs Arch. 78 (1), 41 (1994).
A. Kekulé, Bull. Soc. Chim. Fr. Nouvelle sen [3] 1, 98 (1865).
A. Kekulé, Bull. Acad. R. Belg. [2] 19, 551 (1865).
A. Kekulé, Justus Liebigs Ann. Chem. 137, 129 (1866). See also.
A. Kekulé, Ber. Dtsch. Chem. Ges. 2, 362 (1869).
A. Kekulé, Justus Liebigs Ann. Chem. 162, 77 (1872).
A. Kekulé, Lehrbuch der Organischen Chemie, Enke, Erlangen, Vol. 2, 1866, pp. 514, 515.
A. Crum Brown, Trans. R. Soc. Edinburgh 23, 707 (1864).
A. Crum Brown, Trans. R. Soc. Edinburgh 24, 331 (1866).
A. Crum Brown, J. Chem. Soc. 18, 230 (1865).
A. Kekulé, Z. f. Chem. N. F. 3, 214 (1867); see especially p. 218. Reprinted in ref. 5, Vol. II, p. 525.
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.
A. M. Butlerov, Z. Chem. Pharm. 5, 297 (1862).
A. M. Butlerov, Z. Chem. Pharm. 6, 500 (1863).
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.).
J. H. van’t Hoff, Arch. Ned. Sci. Exactes Nat. 9, 445 (1874).
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.
J. A. Le Bel, Bull. Soc. Chim. Fr. [2], 22, 337 (1874); translated in ref. la, p. 161.
e.g. S. F. Mason. Top. Stereochem. 9, 1 (1976).
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.
J. H. van’t Hoff, La Chimie dans l’Espace, Bazendijk, Rotterdam, 1875, pp. 13-14.
H. Kolbe, J. Prakt. Chem. [2] 15, 473 (1877).
cf. P. H. Hermans, in “van’t Hoff-Le Bel Centennial”, O. B. Ramsey, ed., Am. Chem. Soc, Washington, DC, 1975, p. 123.
C. A. Bischoff, Ber. Dtsch. Chem. Ges. 23, 620 (1890). cf. G. V. Bykov, ref. 26, p. 114.
A. Baeyer, Ber. Dtsch. Chem. Ges. 18, 2269 (1885).
A. Baeyer, Justus Liebigs Ann. Chem. 258, 145 (1890).
H. Sachse, Ber. Dtsch. Chem. Ges. 23, 1363 (1890).
H. Sachse, Z. Phys. Chem. 10, 203 (1892).
O. Aschan, Justus Liebigs Ann. Chem. 271, 262 (1892).
A. Werner, H. E. Conrad, Ber. Dtsch. Chem. Ges. 32, 3046 (1899).
O. Aschan, Chemie der Alicyklischen Verbindungen, Vieweg, Braunschweig, 1905.
E. W. M. Mohr, Chem. Zentralbl. 1915 II, 1065 (Sitzungsber. Heidelberg. Akad. Wiss., Math. Naturwiss. Kl., Abt. A, 1915, 7. Abh.).
E. W. M. Mohr, J. Prakt. Chem. [2] 98, 315 (1918).
E. W. M. Mohr, J. Prakt. Chem. 103, 316 (1922).
W. Hückel, Justus Liebigs Ann. Chem. 441, 1 (1925).
J. Boëseken, H. G. Derx, Reel. Trav. Chim. Pays-Bas 40, 519, 529 (1921).
J. Boëseken, Recl. Trav. Chim. Pays-Bas 40, 553 (1921).
P. H. Hermans, Z. Phys. Chem. 113, 337 (1924).
S. Winstein, N. J. Holness, J. Am. Chem. Soc. 77, 5562 (1955).
S. B. Hendricks, C. Biticke, J. Am. Chem. Soc. 48, 3007 (1926).
R. G. Dickinson, C. Bilicke, J. Am. Chem. Soc. 50, 764 (1928).
R. S. Rasmussen, J. Chem. Phys. 11, 249 (1943).
K. W. F. Kohlrausch, H. Wittek, Z. Phys. Chem. 48B, 177 (1941).
cf. O. Hassel, H. Viervoll, Acta Chem. Scand. 1, 149 (1947).
J. G. Aston, S. C. Schumann, H. L. Fink, P. M. Doty, J. Am. Chem. Soc. 63, 2029 (1941).
R. L. Shriner, R. Adams, C. Marvel, “Stereochemistry” in H. Gilman, ed., Organic Chemistry, 2nd ed., Vol. 1, Wiley, New York, 1943, p. 321.
J. D. Kemp, K. S. Pitzer, J. Chem. Phys. 4, 749 (1936).
J. D. Kemp, K. S. Pitzer, J. Am. Chem. Soc. 59, 276 (1937).
K. S. Pitzer, J. Chem. Phys. 5, 473 (1937).
cf. S. Mizushima, Structure of Molecules and Internal Rotation, Academic Press, New York, 1954.
S. Mizushima, Pure Appl. Chem. 7, 1 (1963).
O. Hassel, Tidsskr. Kjemi Bergves. Metall. 3 [5], 32 (1943); transi, by.
K. Hedberg, Top. Stereochem. 6, 11 (1971).
C. W. Beckett, K. S. Pitzer, R. Spitzer, J. Am. Chem. Soc. 69, 2488 (1947);cf.
E. J. Prosen, W. H. Johnson, F. D. Rossini, J. Res. Natl. Bur. Stand. 39, 173 (1947).
J. E. Leonard, G. S. Hammond, H. E. Simmons, J. Am. Chem. Soc. 97, 5052 (1975).
D. H. R. Barton, Experientia 6, 316 (1950).
D. H. R. Barton, reprinted in Top. Stereochem. 6, 1 (1971).
E. L. Eliel, 100+ Years of Conformational Analysis, chapter 1 in ref. 69, p. 1.
See also D. H. R. Barton, Some Recollections of Gap Jumping, American Chemical Society, Washington, DC, 1991.
E. L. Eliel, From Cologne to Chapell Hill, American Chemical Society, Washington, DC, 1990.
E. L. Eliel, Experientia 9, 91 (1953).
J. Read, W. J. Grubb, J. Chem. Soc. 1934, 1779.
E. L. Eliel, R. S. Ro, Chem. Ind. (London) 1956, 251.
cf. C. H. Bushweller, Stereodynamics of Cyclohexane and Substituted Cyclohexanes. Substituent A Values, chapter 2 in ref. 69, p. 25.
E. L. Eliel, C. A. Lukach, J. Am. Chem. Soc. 79, 5986 (1957).
E. L. Eliel, R. S. Ro, J. Am. Chem. Soc. 79, 5992 (1957).
E. L. Eliel, Chem. Ind. (London) 1959, 568.
F. R. Jensen, D. S. Noyce, C. H. Sederholm, A. J. Berlin, J. Am. Chem. Soc. 82, 1256 (1960).
F. R. Jensen, D. S. Noyce, C. H. Sederholm, A. J. Berlin, J. Am. Chem. Soc. 84, 386 (1962).
E. L. Eliel, S. H. Wilen, Stereochemistry of Organic Compounds, Wiley, New York, 1994, chapter 11.
R. L. Wilier, E. L. Eliel, J. Am. Chem. Soc. 99, 1925 (1977).
E. L. Eliel, D. Kandasamy, C.-Y. Yen, K. D. Hargarve, J. Am. Chem. Soc. 102, 3698 (1980).
E. L. Eliel, K. D. Hargrave, K. M. Pietrusiewicz, M. Manoharan, J. Am. Chem. Soc. 104, 3635 (1982). See also ref. 54, p. 8.
cf. E. L. Eliel, M. C. Knoeber, J. Am. Chem. Soc. 88, 5347 (1966).
cf. E. L. Eliel, M. C. Knoeber, J. Am. Chem. Soc. 90, 3444 (1968).
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.
E. Juaristi, ed., Conformational Behavior of Six-membered Rings, VCH, New York, 1995.
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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
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