Bulletin of the Korean Chemical Society

  • 제29권6호
  • /
  • Pages.1195-1198
  • /
  • 2008
  • /
  • 0253-2964(pISSN)
  • /
  • 1229-5949(eISSN)
대한화학회 (Korean Chemical Society)
권호 표지
DOI QR코드

DOI QR Code

A Mechanistic Study on the Nucleophilic Addition Reactions of Benzylamines to the Activated Olefins

  • Oh, Hyuck-Keun (Department of Chemistry, Research Institute of Physics and Chemistry, Chonbuk National University)
  • 발행 : 2008.06.20
PDF 다운로드
⟨ 이전 논문 다음 논문 ⟩

초록

Kinetic studies of the additions of benzylamines to a noncyclic dicarbonyl group activated olefin, methyl $\alpha$-acetyl-$\beta$ -phenylacrylates (MAP), in acetonitrile at 30.0 ${^{\circ}C}$ are reported. The rates are lower than those for the cyclic dicarbonyl group activated olefins. The addition occurs in a single step with concurrent formation of the $C_\alpha$ -N and $C_\beta$ -H bonds through a four-center hydrogen bonded transition state. The kinetic isotope effects ($k_H/k_D$ > 1.0) measured with deuterated benzylamines ($XC_6H_4CH_2ND_2$) increase with a stronger electron acceptor substituent ($\delta\sigma$ X > 0) which is the same trend as those found for other dicarbonyl group activated series (1-4). The sign and magnitude of the cross-interaction constant, ρXY, is comparable to those for the normal bond formation processes in the $S_N2$ and addition reactions. The relatively low ${\Delta}H^\neq$ and large negative ${\Delta}S^\neq$ values are also consistent with the mechanism proposed.

키워드

참고문헌

  1. Oh, H. K.; Yang, J. H.; Sung, D. D.; Lee, I. J. Chem. Soc. Perkin Trans. 2 2000, 101
  2. Oh, H. K.; Yang, J. H.; Lee, H. W.; Lee, I. J. Org. Chem. 2000, 65, 2188 https://doi.org/10.1021/jo991823d
  3. Oh, H. K.; Kim, T. S.; Lee, H. W.; Lee, I. J. Chem. Soc. Perkin Trans. 2 2002, 282
  4. Oh, H. K.; Yang, J. H.; Hwang, Y. H.; Lee, H. W.; Lee, I. Bull. Korean Chem. Soc. 2002, 23, 221 https://doi.org/10.5012/bkcs.2002.23.2.221
  5. Oh, H. K.; Kim, T. S.; Lee, H. W.; Lee I. Bull. Korean Chem. Soc. 2003, 24, 193 https://doi.org/10.5012/bkcs.2003.24.2.193
  6. Oh, H. K.; Yang, J. H.; Lee, H. W.; Lee, I. J. Org. Chem. 2000, 65, 5391 https://doi.org/10.1021/jo000512w
  7. Oh, H. K.; Kim, I. K.; Lee, H. W.; Lee, I. J. Org. Chem. 2004, 69, 3806 https://doi.org/10.1021/jo034370s
  8. Bernasconi, C. F. Acc. Chem. Res. 1987, 20, 301 https://doi.org/10.1021/ar00140a006
  9. Bernasconi, C. F. Tetrahedron 1989, 45, 4017 https://doi.org/10.1016/S0040-4020(01)81304-1
  10. Lee, I. Chem. Soc. Rev. 1990, 19, 317 https://doi.org/10.1039/cs9901900317
  11. Lee, I. Adv. Phys. Org. Chem. 1992, 27, 57
  12. Lee, I.; Lee, H. W. Coll. Czech Chem. Commun. 1999, 64, 1529 https://doi.org/10.1135/cccc19991529
  13. Ritchie, C. D. In Solute-Solvent Interactions; Coetzee, J. F.; Ritchie, C. D., Eds.; Marcel Dekker: New York, 1969; Chapter 4
  14. Coetzee, J. F. Prog. Phys. Org. Chem. 1967, 4, 54
  15. Spillane, W. J.; Hogan, G.; McGrath, P.; King, J.; Brack, C. J. Chem. Soc. Perkin Trans. 2 1996, 2099
  16. Lee, I.; Kim, C. K.; Han, I. S.; Lee, H. W.; Kim, W. K.; Kim, Y. B. J. Phys. Chem. B 1999, 103, 7302 https://doi.org/10.1021/jp991115w
  17. Bernasconi, C. F.; Stronach, M. W. J. Am. Chem. Soc. 1991, 113, 2222 https://doi.org/10.1021/ja00006a046
  18. Pross, A. Theoretical and Physicals of Organic Reactivity; Wiley: New York, 1995; Chapter 5
  19. Dewar, M. J. S.; Dougherty, R. C. The PMO Theory of Organic Chemistry; Plenum: New York, 1975; Chapter 5
  20. Pross, A. Adv. Phys. Org. Chem. 1997, 14, 69
  21. Buncel, E.; Wilson, H. J. Chem. Educ. 1987, 64, 475 https://doi.org/10.1021/ed064p475
  22. Horning, E. C.; Fish, M. S.; Walker, G. N. Organic Synthesis, Collect.; Wiley: New York, 1983; Vol. 4, p 408
  23. Ku, M. H.; Oh, H. K.; Ko, S. Bull. Korean Chem. Soc. 2007, 28, 1217 https://doi.org/10.5012/bkcs.2007.28.7.1217
  24. Oh, H. K.; Ku, M. H. Bull. Korean Chem. Soc. 2006, 27, 1873 https://doi.org/10.5012/bkcs.2006.27.11.1873
  25. Hansch, C.; Leo, A.; Taft, R. W. Chem. Rev. 1991, 91, 165 https://doi.org/10.1021/cr00002a004
  26. Fischer, A.; Galloway, W. J.; Vaughan, J. J. Chem. Soc. 1964, 3588 https://doi.org/10.1039/jr9640003588
  27. Oh, H. K.; Lee, J. Y.; Lee, I. Bull. Korean Chem. Soc. 1998, 19, 1198
  28. Wiberg, K. B. Physical Organic Chemistry; Wiley: New York, 1964; p 378

피인용 문헌

  1. Effects of substituents on activation parameter changes in the Michael-type reactions of nucleophilic addition to activated alkenes and alkynes in solution vol.147, pp.2, 2016, https://doi.org/10.1007/s00706-015-1622-5
  2. Kinetics and Mechanism of Addition of Benzylamines to Methyl α-Cyanocinnamates in Acetonitrile vol.30, pp.8, 2008, https://doi.org/10.5012/bkcs.2009.30.8.1887
  3. Michael-type Reactions of 1-(X-substituted phenyl)-2-propyn-1-ones with Alicyclic Secondary Amines in MeCN and H2O: Effect of Medium on Reactivity and Transition-State Structure vol.31, pp.5, 2008, https://doi.org/10.5012/bkcs.2010.31.5.1199
  4. Inner Workings of a Cinchona Alkaloid Catalyzed Oxa‐Michael Cyclization: Evidence for a Concerted Hydrogen‐Bond‐Network Mechanism vol.19, pp.7, 2008, https://doi.org/10.1002/chem.201203505