Synthesis of New ${\alpha}$-Amidoketenes Using Malonyl Dihalide

Malonyl Dihalide를 이용한 새로운 ${\alpha}$-Amidoketenes의 합성

  • 오미정 (덕성여자대학교 약학대학) ;
  • 박명숙 (덕성여자대학교 약학대학)
  • Received : 2011.02.08
  • Accepted : 2011.03.03
  • Published : 2011.04.30

Abstract

We synthesized new ${\alpha}$-amidoketenes using dehydrochlorination from anilines, triethylamine and malonyl dichloride under $0^{\circ}C$. The utility of ketenes in both laboratory and industrial practice was quickly recognized, and these species have been extensively utilized, including as pharmaceutical intermediates and anti-cancer agents. All synthetic process from anilines to ${\alpha}$-amidoketenes could be carried out by one-pot reaction. Synthetic ketenes 2a~f were identified using NMR and IR spectrum. Formation of ketenes was undertaken with dropping of malonyl dichloride at $0^{\circ}C$ in methylene chloride for 0.5~4 h. Using malonyl dichloride was better than using diethyl malonate as a synthetic reagents for the ketenes.

Keywords

References

  1. Tidwell, T. T. : Ketenes, 2nd, John Wiley & Sons, Inc. p. 1 (2006).
  2. Williams, A. and Douglas, K. T. : Elimination-Addition Mechanism of Acyl Transfer Reactions, Chem. Rev. 75, 627 (1975). https://doi.org/10.1021/cr60297a006
  3. Taggi, A. E., Wack, H., Hafez, A. M., France, S. and Lectka, T. : Generation of ketenes from acid chlorides using NaH/Crown ether shuttle-deprotonation for use in asymmetric catalysis. Org. Lett. 4, 627 (2002). https://doi.org/10.1021/ol0172525
  4. Bottcher, A., Debaerdemacker, T., Radziszewski, J. G. and Friedrichsen, W. : Darstellung von 1-Oxo-1H-pyrazolo[1,2- a][1,2,4]triazol-4-ium-3-olaten. Eine Ring-Ketten-Tautomerie in der Reihe bicyclischer dipolarer Heterocyclen. Chem. Ber. 121, 895 (1988). https://doi.org/10.1002/cber.19881210513
  5. Wentrup, C., Rao, R., Frank, W., Fulloon, B. E., Moloney, D. W. J. and Mosandl, T. : Aryliminopropadienone Camidoketenimine amidinoketene-2-aminoquinoline cascades and the ynamine-isocyanate reaction. J. Org. Chem. 64, 3608 (1999).
  6. Finnerty, J., Andraos, J., Yamamoto, Y., Wong, M. W. and Wentrup, C. : Facile 1,3-Shift of chlorine in a Chlorocarbonylketene. J. Am. Chem. Soc. 120, 1701 (1998). https://doi.org/10.1021/ja973242g
  7. Sheibani, H., Bernhardt, P. and Wentrup, C. : Mesoionic 1,3- oxazinium olates. Rearrangement to acylketenes and 3- azabicyclo[3.1.1]heptanetriones. J. Org. Chem. 70, 5859 (2005). https://doi.org/10.1021/jo050428m
  8. Bornemann, H. and Wentrup, C. : Energy profiles for ketene cyclizations. Interconversion of 1,3-oxazin-6-ones mesoionic 1,3-oxazinium olates and acylketenes, imidoylketenes, oxoketenimines, and cyclization products. J. Org. Chem. 70, 5862 (2005). https://doi.org/10.1021/jo050429e
  9. Ussing, B. R., Hang, C. and Singleton, D. A. : Dynamic effects on the periselectivity, rate, isotope effects, and mechanism of cycloadditions of ketenes with cyclopentadiene. J. Am. Chem. Soc. 128, 7594 (2006). https://doi.org/10.1021/ja0606024
  10. Tidwell, T. T. : Catalytic asymmetric esterification of ketenes. Angew. Chem. Int. Ed. 44, 6812 (2005). https://doi.org/10.1002/anie.200501849
  11. Fu, G. : Enantioselective nucleophilic catalysis with "Planar- Chiral" heterocycles. Acc. Chem. Res. 33, 412 (2000). https://doi.org/10.1021/ar990077w
  12. Gupta, V. P., Sharma, A. and Agrawal, S. G. : Conformations, chemical reactivities and spectroscopic characteristics of some Di-substituted ketenes: An ab initio study. Bull. Korean Chem. Soc. 27, 1297 (2006). https://doi.org/10.5012/bkcs.2006.27.9.1297
  13. Yan, S. J., Huang, C., Zeng, X. H., Huang, R. and Lin, J. : Solvent-free, microwave assisted synthesis of polyhalo heterocyclic ketene aminals as novel anti-cancer agents. Bioorg. Med. Chem. Lett. 20, 48 (2010). https://doi.org/10.1016/j.bmcl.2009.11.044