Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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(-)-β-Narcotine: A Facile Synthesis and the Degradation with Ethyl Choroformate

  • Published : 2002.11.20
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Abstract

$(-)-\beta-Narcotine$ (6), a phthalideisoquinoline alkaloid, was synthesized conveniently by the direct condensation of cotarnine (1) and iodomeconine (2) prepared by aromatic iodination using thallium trifluoroacetate/KI and by the successive reduction of resulting $iodo-{\beta}-narcotine$ (5) with aluminum amalgam. Its structure including a stereochemistry was confirmed by instrumental analyses. This synthetic alkaloid was degraded with ethyl chloroformate at room temperature to afford the chloro-carbamate 6b as a crystalline intermediate, which was unexpectedly converted into the carbinol 8 by exchange of Cl with OH of water contained in the solvents and the ethoxy-carbamate 9, probably because of ethanol added to chloroform as a solvent stabilizer during the purification by column chromatography.

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References

  1. Perkin, W. H., Jun.; Robinson, R. J. Chem. Soc. 1911, 99, 775. https://doi.org/10.1039/ct9119900775
  2. Hope, E.; Robinson, R. J. Chem. Soc. 1914, 105, 2085. https://doi.org/10.1039/ct9140502085
  3. Kerekes, V. P.; Bognar, R. J. Prak. Chem. 1971, 313, 923. https://doi.org/10.1002/prac.19713130518
  4. Varga, Z.; Blasko, G.; Dornyei, G.; Szantay, C. Acta Chim. Hung. 1991, 128, 831.
  5. Freund, M.; Frankforter, G. B. Justus Liebigs Ann. Chem. 1893, 277, 20. https://doi.org/10.1002/jlac.18932770103
  6. Blasko, G.; Elango, V.; Sener, B.; Freyer, A. J.; Shamma, M. J. Org. Chem. 1982, 47, 880. https://doi.org/10.1021/jo00344a025
  7. Klotzer, W.; Teitel, S.; Brossi, A. Monatsh. Chem. 1972, 103, 1210. https://doi.org/10.1007/BF00905197
  8. Iwasa, K.; Kamigauchi, M.; Sugiura, M.; Takao, N. J. Nat. Prod. 1987, 50, 1083. https://doi.org/10.1021/np50054a012
  9. Kerekes, P.; Gaal, G. Acta Chim. Acad. Sci. Hung. 1980, 103, 343.
  10. Klotzer, W.; Teitel, S.; Brossi, A. Helv. Chim. Acta 1972, 55, 2228. https://doi.org/10.1002/hlca.19720550644
  11. Lee, Dong-Ung; Eibler, E.; Mayer, K. K.; Wiegrebe, W. Chem. Pharm. Bull. 1995, 43, 1995. https://doi.org/10.1248/cpb.43.1995
  12. Blasko, G.; Gula, D. J.; Shamma, M. J. Nat. Prod. 1982, 45, 105. https://doi.org/10.1021/np50020a001
  13. Lee, Dong-Ung; Iwasa, K.; Kamigauchi, M.; Takao, N.; Wiegrebe, W. Chem. Pharm. Bull. 1991, 39, 1944. https://doi.org/10.1248/cpb.39.1944
  14. Okamoto, Y.; Dirnberger, D.; Burgemeister, T.; Dannhardt, G.; Wiegrebe, W. Arch. Pharm. (Weinheim) 1986, 319, 1122. https://doi.org/10.1002/ardp.19863191212
  15. Wilson, J. W., III.; Zirkle, C. L.; Anderson, E. L.; Stehle, J. J.; Ullyot, G. E. J. Org. Chem. 1951, 16, 792. https://doi.org/10.1021/jo01145a021
  16. Marshall, (Miss) M. A.; Pyman, F. L.; Robinson, R. J. Chem. Soc. 1934, 1315. https://doi.org/10.1039/jr9340001315
  17. Battersby, A. R.; Spenser, H. J. Chem. Soc. 1965, 1087. https://doi.org/10.1039/jr9650001087
  18. Lee, Dong-Ung; Iwasa, K.; Kamigauchi, M.; Takao, N.; Wiegrebe, W. Chem. Pharm. Bull. 1991, 39, 1944. https://doi.org/10.1248/cpb.39.1944
  19. Shamma, M.; Georgiev, V. St. Tetrahedron Lett. 1974, 2339.
  20. Gadamer, J.; Knoch, F. Arch. Pharm. (Weinheim) 1921, 259, 135. https://doi.org/10.1002/ardp.19212590112
  21. Lee, Dong-Ung; Wiegrebe, W. Bull. Korean Chem. Soc. 1991, 12, 373.

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