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Diastereospecific Recognition of Dyes by Salt Crystals: A Case of Plundered Stereochemistry in Postwar Europe

  • Bart Kahr
  • Michael P. Kelley
Part of the NATO ASI Series book series (ASIC, volume 473)

Abstract

As early as March 1944, the British were making plans for the occupation of Germany.1 A chief concern of these planners was the capture of technologies that would assist the Allied nations in the defeat of Japan and in the postwar economy. The assets of IG Farben, the chemical conglomerate that enabled Germany to fight in the First and Second World Wars, were among the most sought after targets. In this paper we discuss how incomplete crystal structures of triarylmethane dyes, captured from IG Farben by British Intelligence, led to an incorrect analysis of the stereospecific recognition of these dyes by simple ionic salts. We review our work on the determination of these stereospecific association mechanisms within the context of earlier errors and remind the reader of consequential political and economic events that serve as the requisite background for a complete understanding of an otherwise insignificant stereochemical puzzle.

Keywords

Crystal Violet Ammonium Nitrate Twist Angle Aryl Ring Acid Fuchsin 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

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References

  1. 1.
    Stokes, R. G. (1988) Divide and Prosper: The Heirs of I. G. Farben under Allied Authority, 1945-1951, University of California Press, Berkeley.Google Scholar
  2. 2.
    Kahr, B.; Chow, J. K.; Peterson, M. L. (1994) Organic Hourglass Inclusions, J. Chem. Ed. 71, 584–586.CrossRefGoogle Scholar
  3. 3.
    Kelley, M. P.; Janssens, B.; Kahr, B.; Vetter, W. (1994) Recognition of Dyes by K2SO4 Surfaces: Choosing Organic Guests for Simple Salts, J. Am. Chem. Soc. 116, 5519–5520.CrossRefGoogle Scholar
  4. 4.
    Dudley, M.; Vetter, W.; Kahr, B. (1993) X-ray Topographic Studies of Hourglass Inclusions, National Synchrotron Light Source Report, (eds. Hurlburt, S. L.; Lazarz, M. L.) Brookhaven National Laboratory, Upton, New York.Google Scholar
  5. 5.
    Kelley, M. P.; Kahr, B. to be submitted for publication.Google Scholar
  6. 6.
    Elliott, D.; Rifani, M.; Jay, M. J.; Kelley, M. P.; Kahr, B. to be submitted for publication.Google Scholar
  7. 7.
    Dewar, M. J. S.; Zoebisch, E. G.; Healy, E. F.; Stewart, J. J. P. (1985) AMI: A New General Purpose Quantum Mechanical Molecular Model, J. Am. Chem. Soc. 107, 3902–3909; Stewart, J. J. P. Quantum Chemistry Program Exchange, Bloomington, Indiana, No. 455.CrossRefGoogle Scholar
  8. 8.
    Ridley, J.; Zerner, M. C. (1973) An Intermediate Neglect of Differential Overlap Technique for Spectroscopy: Pyrrole and the Azines, Theor. Chim. Acta, 32, 111–134; (1976) Triplet States via Intermediate Neglect of Differential Overlap: Benzene, Pyridine, and the Diazines, 42, 223–236.CrossRefGoogle Scholar
  9. 9.
    For reviews of the stereochemistry of molecular propellers, see: Mislow, K.; Gust, D.; Finocchiaro, P.; Boettcher, R. J. (1974) Fortschr. Chem. Forsch. 47, 1–28; Mislow, K. (1976) Acc. Chem. Res. 9, 26–33.Google Scholar
  10. 10.
    For biographical information and an almost complete bibliography see: Deer, W. A. (1961) Memorial of Harold Eugene Buckley, Am. Min. 46, 481.Google Scholar
  11. 11.(a)
    Buckley, H. E. (1933) Systematic Habit-Variation in KCIO3 Crystals Produced by Dyes, Zeit Krist. 85, 58–73Google Scholar
  12. 11.(b)
    (1934) Molecular Configuration and its Relation to Modification of Crystal-Growth, 88, 381–411Google Scholar
  13. 11.(c)
    (1935) Some New Features in Habit-Modification Shown by KCIO4 Crystals, 91, 375–401.Google Scholar
  14. 12.
    Buckley, H. E. (1951) Studies in the Growth and Habit Modification of Crystals, Memoirs and Proceedings of the Manchester Literary and Philosophical Society, 92, 77–123.Google Scholar
  15. 13.
    For our review of Buckley’s habit modification studies, see: Kelley, M.; Chow, J. K.; Kahr, B. (1994) Critical Evaluation of Dyes as Crystal Growth Inhibitors, Mol. Cryst. Liq. Cryst. 242, 201–214.CrossRefGoogle Scholar
  16. 14.
    Buckley, H. E. (1934) The Oriented Inclusion of Impurities in Crystals, Zeit. Krist. 88, 248–255.Google Scholar
  17. 15.
    During the end of his career, Buckley began to use optical spectroscopies to identify dye inclusions in salts. He published one spectrum and declared that “A new branch of Chemistry seems nearby” (ref 11).Google Scholar
  18. 16.
    Butchart, A.; Whetstone, J. (1949) The Effect of Dyes on the Crystal Habits of Some Oxy-Salts, Discussions of the Faraday Society, 243–254; Whetstone, J. (1951) Modification of Crystal Habit of Inorganic Salts with Dyes, Nature, 168, 663-664.Google Scholar
  19. 17.
    Whetstone, J. (1952) Solution to the Caking Problem of Ammonium Nitrate and Ammonium Nitrate Explosives, Ind. Eng. Chem. 44, 2663–2667; British Patent (1953) 665, 478.CrossRefGoogle Scholar
  20. 18.
    Davey, R. J.; Polywka, L. A.; Maginn, S. M. (1991) Adv. Ind. Cryst. (eds Garside et al.) Butterworth-Heinemann, Oxford, pp 150–165.Google Scholar
  21. 19.
    Whetstone, J. (1954) The Adsorption of Dyes by Crystals, Discussions of the Faraday Society, 132–140.Google Scholar
  22. 20.
    Whetstone, J. (1956) Crystal Symmetry, and the Adsorption of Dyes by Growing Crystals. Part I. Ammonium Nitrate IV. J. Chem. Soc. 4841–4847.Google Scholar
  23. 21.
    Whetstone, J. (1955) The Crystal Habit Modification of Inorganic Salts with Dyes: Part 2. — The Relationship between the Structure of Crystal and Habit Modifying Dyes, Trans. Faraday Soc. 51, 1142–1153.CrossRefGoogle Scholar
  24. 22.
    Travis, A. S. (1993) The Rainbow Makers: The Origins of the Synthetic Dyestuffs Industry in Western Europe, Lehigh University Press, Bethlehem; Beer, J. J. (1959) The Emergence of the German Dye Industry, Urbana, University of Illinois Press; Haber, L. F. (1958) The Chemical Industry During the Nineteenth Century, Clarendon, Oxford.Google Scholar
  25. 23.
    There is an excellent and extensive literature on the synthetic dyestuffs industry in general and IG Farben in particular. We have tried to select representative citations for each of the following 5 subsections. There is a great deal of redundancy in the information contained within the acknowledged monographs. Much of the information can be found in several places.Google Scholar
  26. 24.
    de Sénarmont, H. (1854) Versuche über die Künstliche Erzeugung von polychromismus in krystallisirten Substanzen, Ann. Phys. (Leipzig) 167, 491–504.CrossRefGoogle Scholar
  27. 25.
    Haber, L. F. (1971) The Chemical Industry, 1900-1930, Clarendon, Oxford.Google Scholar
  28. 26.
    Two other companies, Griesheim-Elecktron and Farbwerk Mühlheim, were later added to IG.Google Scholar
  29. 27.
    Borkin, J. (1978) The Crime and Punishment of I G Farben, The Free Press, NY.Google Scholar
  30. 28.
    Ibid, p 29.Google Scholar
  31. 29.(a)
    Sasuly, R. (1947) I G Farben, Boni and Gaer, New YorkGoogle Scholar
  32. 29.(b)
    Hayes, P. (1987) Industry and Ideology. I G Farben in the Nazi Era, Cambridge University Press, Cambridge.Google Scholar
  33. 30.
    ref 29a, p 88.Google Scholar
  34. 31.
    Among IG’s most notorious crimes was the production, through one of its subsidiaries, of the insecticide Zyklon B. The prussic acid in Zyklon B was ordinarily accompanied by an odoriferous compound to alert humans to its presence. The SS ordered large amounts without the indicator. This modified poison product was better suited to the mass murder of those not forcibly engaged in the war-time chemical industry, among others.27 Google Scholar
  35. 32.
    Gimbel, J. (1990) Science, Technology, and Reparations. Exploitation and Plunder in Postwar Germany, Stanford University Press, Stanford.Google Scholar
  36. 33.
    DuBois, J. E. Jr. (1952) The Devil’s Chemists, The Beacon Press, Boston.Google Scholar
  37. 34.
    Numerical Index to the Bibliography of Scientific and Industrial Reports, Vols. 1-10, 1946-1948, (1949) Ann Arbor, Edwards Bros.Google Scholar
  38. 35.
    Maynard, C. W. (1955) The Chemistry of Synthetic Dyes and Pigments, (ed. Lubs, H. A.) ACS, New York.Google Scholar
  39. 36.
    ref 31, pp 11-12.Google Scholar
  40. 37.
    Krebs was a leading crystallographer who started an X-ray diffraction school in Bonn and later wrote a popular book: Krebs, H. (1968) Fundamentals of Inorganic Crystal Chemistry (trans. Walter, P. H. L.) McGraw-Hill, London.Google Scholar
  41. 38.
    Krebs sites a discussion between two contemporaries: Eistert, B. (1938), Tautomerie and Mesomerie, Ferdinand Enke, Stuttgart; and Wizinger, R. (1933) Organische Farbstoffe, Ferdinand Dümmlers, Berlin.Google Scholar
  42. 39.
    “Infolge Einberufung zur Wehrmacht konnte sie nicht beendigt werden.”Google Scholar
  43. 40.
    Ewald, P. P. (1962) Fifty Years of X-ray Diffraction, International Union of Crystallography, International Union of Crystallography, Utrecht.CrossRefGoogle Scholar
  44. 41.
    Stora, C.; Eller, G. (1949) Caractères radiocrystallographiques de quelques derives du triphénylméthane, Comp. Rend. 229, 766–768; Stora, C. (1958) Sur la stéoréchimie aux rayons X de la pararosaniline et du violet hexaméthylé. Comp. Rend. 246, 1693-1695.Google Scholar
  45. 42.
    Lueck, H. B.; McHale, J. L.; Edwards, W. D. (1992) Symmetry-Breaking Solvent Effects on the Electronic Structure and Spectra of a Series of Triphénylméthane Dyes, J. Am. Chem. Soc. 114, 2342–2348.CrossRefGoogle Scholar
  46. 43.
    Angeloni, L.; Smulevich, G.; Marzocchi, M. P. (1979) Resonance Raman Spectrum of Crystal Violet, J. Raman Spec. 24, 305–310.CrossRefGoogle Scholar
  47. 44.
    Lewis, G. N.; Magel, T. T.; Lipkin, D. (1942) Isomers of Crystal Violet Ion. Their Absorption and Re-emission of Light, J. Am. Chem. Soc. 42, 1774–1782.CrossRefGoogle Scholar
  48. 45.
    Brunings, K. J.; Corwin. A. H. (1944) Effect of Substituents on the Structure of Dipyrrylmethenes. Some Relationships between the Dipyrryl-and the Triphénylméthane Dyes, J. Am. Chem. Soc. 66, 337–342.CrossRefGoogle Scholar
  49. 46.
    Seel, F. (1943) Zur quantentheoretischen Begründung der Stabilität von Kohlenstoffradikalen, Naturwissenschaften, 31, 505. His contributions are also summarized by Hoffmann et al. See: Hoffmann, R.; Bissell, Farnum, D. G. (1969) The Balance of Steric and Conjugative Effects in Phenyl-Substituted Cations, Radicals, and Anions, J. Phys. Chem. 73, 1789-1800.CrossRefGoogle Scholar
  50. 47.
    Szwarc, M. (1947) The Resonance Energy of the Benzyl Radical, Discussions of the Faraday Society, 2, 39–46.CrossRefGoogle Scholar
  51. 48.
    Sharp, D. W. A.; Sheppard, N. (1957) Complex Fluorides. Part VIII. The Preparation and Properties of Salts of the Triphenylmethyl Cation: The Infrared Spectrum and Configuration of the Ion, J. Chem. Soc. 674–679.Google Scholar
  52. 49.
    For an overview of triarylmethyl radical crystal structures see: Kahr, B.; Van Engen, D.; Gopalan, P. (1993) Crystal Structure and Magnetic Susceptibility of a Hydrocarbon Free Radical: Tris(3, 5-di-tert-butylphenyl)methyl, Chem. Mat. 5, 729–732.CrossRefGoogle Scholar
  53. 50.
    Gomes de Mesquita, A. H.; MacGillavry, C. H.; Eriks, K. (1965) The Structure of Triphenylmethyl Perchlorate at 85°C, Acta Cryst. 18, 437–443.CrossRefGoogle Scholar
  54. 51.
    Andersen, F.; Klewe, B. (1965) Structure Investigation of Tri-p-methoxyphenylmethyl Carbonium Ion, Acta Chem. Scand. 19, 791–796.CrossRefGoogle Scholar
  55. 52.
    Koh, L.L.; Eriks, K. (1971) The Crystal Structure of a Stable Carbonium Ion, Tri(p-aminophenyl)carbonium Perchlorate, (H2NC6H4)3C+ Ç104 -, Acta Cryst. Sect. B. B27, 1405–1413.CrossRefGoogle Scholar
  56. 53.
    Wingate, P. J. (1982) The Colorful DuPont Company, Serendipity Press, Wilmington, Delaware.Google Scholar
  57. 54.
    Spangler, B. D.; Vanysek, P.; Hernandez, I. C.; Rogers, R. D. J. (1989) Structure of Crystal Violet Tetraphenylborate, Cryst. Spectr. Res. 19, 589–596.CrossRefGoogle Scholar
  58. 55.
    If and when we find the trigonal phase, we will report the details of the monoclinic structure at that time. Atomic coordinates and structure factors for the monohydrate may be obtained by writing to the authors directly.Google Scholar

Copyright information

© Springer Science+Business Media Dordrecht 1995

Authors and Affiliations

  • Bart Kahr
    • 1
  • Michael P. Kelley
    • 1
  1. 1.Department of ChemistryPurdue UniversityWest LafayetteUSA

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