View PDF Version
 
DOI: 10.1039/A801540F (Paper) Reference Section for: J. Chem. Soc., Perkin Trans. 2, 1998, 1329-1332

Kinetics and mechanism of the aminolysis of phenyl cyclopropanecarboxylates in acetonitrile

(Note: The full text of this document is currently only available in the PDF Version )

Han Joong Koh, Chul Ho Shin, Hai Whang Lee and Ikchoon Lee

Abstract

Kinetic studies of the reaction of Z-phenyl cyclopropanecarboxylates with X-benzylamines in acetonitrile at 55.0 °C have been carried out. The reaction proceeds by a stepwise mechanism in which the rate-determining step is the breakdown of the zwitterionic tetrahedral intermediate, T±, with a hydrogen-bonded four-center type transition state (TS). These mechanistic conclusions are drawn based on (i) the large magnitude of ρX and ρZ, (ii) the normal kinetic isotope effects (kH/kD > 1.0) involving deuterated benzylamine nucleophiles, (iii) the positive sign of ρXZ and the larger magnitude of ρXZ than that for normal SN2 processes, and lastly (iv) adherence to the reactivity–selectivity principle (RSP) in all cases.

References

  1. (a) H. K. Oh, C. H. Shin and I. Lee, J. Chem. Soc., Perkin Trans. 2, 1993, 2411 RSC; (b) H. J. Koh, H. C. Lee and H. W. Lee, Bull. Korean Chem. Soc., 1995, 16, 839 CAS; (c) H. K. Oh, C. H. Shin and I. Lee, J. Chem. Soc., Perkin Trans. 2, 1995, 1169 RSC; (d) H. K. Oh, C. H. Shin and I. Lee, Bull. Korean Chem. Soc., 1995, 16, 657 CAS; (e) H. J. Koh, T. H. Kim, B.-S. Lee and I. Lee, J. Chem. Res., 1996, (S) 482; (M) 2741 Search PubMed; (f) H. J. Koh, S. I. Kim, B. C. Lee and I. Lee, J. Chem. Soc., Perkin Trans. 2, 1996, 1353 RSC; (g) H. J. Koh, J.-W. Lee, H. W. Lee and I. Lee, New J. Chem., 1997, 21, 447 Search PubMed; (h) H. K. Oh, S. Y. Woo, C. H. Oh, Y. S. Park and I. Lee, J. Org. Chem., 1997, 62, 5780 CrossRef CAS; (i) H. J. Koh, J.-W. Lee, H. W. Lee and I. Lee, Can. J. Chem., in the press Search PubMed.
  2. (a) P. M. Bond, E. A. Castro and R. B. Moodie, J. Chem. Soc., Perkin Trans. 2, 1976, 68 RSC; (b) M. J. Cresser and W. P. Jencks, J. Am. Chem. Soc., 1977, 99, 6963; 6970 CrossRef CAS; (c) E. A. Castro and M. Freudenberg, J. Org. Chem., 1980, 45, 906 CrossRef CAS; (d) C. Castro and E. A. Castro, J. Org. Chem., 1981, 46, 2939 CrossRef CAS; (e) E. A. Castro and G. B. Steinfort, J. Chem. Soc., Perkin Trans. 2, 1983, 453 RSC; (f) E. A. Castro and C. L. Santander, J. Org. Chem., 1985, 50, 3595 CrossRef CAS; (g) E. A. Castro and C. Ureta, J. Org. Chem., 1989, 54, 2153 CrossRef CAS; (h) E. A. Castro and C. Ureta, J. Org. Chem., 1990, 55, 1676 CrossRef CAS; (i) E. A. Castro and C. Ureta, J. Chem. Soc., Perkin Trans. 2, 1991, 63 RSC; (j) E. A. Castro, F. Ibanez, A. M. Saitua and J. G. Santos, J. Chem. Res., 1993, (S) 56; (M) 0317 Search PubMed; (k) E. A. Castro, M. Salas and J. G. Santos, J. Org. Chem., 1994, 59, 30 CrossRef CAS; (l) E. A. Castro, M. I. Pizarro and J. G. Santos, J. Org. Chem., 1996, 61, 5982 CrossRef CAS; (m) E. A. Castro, M. Cubillos and J. G. Santos, J. Org. Chem., 1996, 61, 3501 CrossRef CAS; (n) E. A. Castro and C. A. Araneda, J. Org. Chem., 1997, 62, 126 CrossRef CAS.
  3. (a) E. Buncel and I. H. Um, J. Chem. Soc., Chem. Commun., 1986, 595 RSC; (b) E. Buncel, I. H. Um and S. Hoz, J. Am. Chem. Soc., 1989, 111, 971 CrossRef CAS; (c) I. H. Um, G. J. Lee, H. W. Yoon and D. S. Kwon, Tetrahedron Lett., 1992, 33, 2023 CrossRef CAS; (d) I. H. Um, H. W. Yoon, J. S. Lee, H. J. Moon and D. S. Kwon, J. Org. Chem., 1997, 62, 5939 CrossRef CAS.
  4. (a) S. Ba-Saif, A. K. Luthra and A. Williams, J. Am. Chem. Soc., 1987, 109, 6362 CrossRef CAS; (b) A. Williams, Adv. Phys. Org. Chem., 1992, 27, 1 CAS; (c) J. March, Advanced Organic Chemistry, Wiley, New York, 4th edn., 1992 Search PubMed; (d) D. Stefanidis, S. Cho, S. Dhe-Paganon and W. P. Jencks, J. Am. Chem. Soc., 1993, 115, 1650 CrossRef CAS; (e) A. H. M. Renfrew, J. A. Taylor, J. M. J. Whitmore and A. Williams, J. Chem. Soc., Perkin Trans. 2, 1994, 2383 RSC; (f) S. Ba-Saif, A. K. Luthra and A. Williams, J. Am. Chem. Soc., 1994, 23, 93; (g) N. R. Cullum, A. H. Renfrew, D. Rettura, J. A. Taylor, J. M. J. Whitmore and A. Williams, J. Am. Chem. Soc., 1995, 117, 9200 CrossRef CAS.
  5. F. M. Menger and J. H. Smith, J. Am. Chem. Soc., 1972, 94, 3824 CrossRef CAS.
  6. (a) D. J. Palling and W. P. Jencks, J. Am. Chem. Soc., 1984, 106, 4869 CrossRef CAS; (b) M. Jedrzejczak, R. E. Motie, D. P. N. Satchell, R. S. Satchell and W. N. Wassef, J. Chem. Soc., Perkin Trans. 2, 1994, 1471 RSC; (c) T. H. Kim, C. Hu, B.-S. Lee and I. Lee, J. Chem. Soc., Perkin Trans. 2, 1995, 2257 RSC; (d) K. H. Yew, H. J. Koh, H. W. Lee and I. Lee, J. Chem. Soc., Perkin Trans. 2, 1995, 2263 RSC.
  7. (a) I. Lee, Bull. Korean Chem. Soc., 1994, 15, 985 CAS; (b) D. Lee, C. K. Kim and I. Lee, Bull. Korean Chem. Soc., 1995, 16, 1203 CAS; (c) I. Lee, D. Lee and C. K. Kim, J. Phys. Chem. A, 1997, 101, 879 CrossRef CAS.
  8. (a) I. Lee, Chem. Soc. Rev., 1990, 19, 317 RSC; (b) I. Lee, Adv. Phys. Org. Chem., 1992, 27, 57 CAS.
  9. I. Lee, B.-S. Lee, H. J. Koh and B. D. Chang, Bull. Korean Chem. Soc., 1995, 16, 277 CAS.
  10. H. Neuvonen, J. Chem. Soc., Perkin Trans. 2, 1995, 951 RSC.
  11. H. Neuvonen, J. Chem. Soc., Perkin Trans. 2, 1987, 159 RSC.
  12. O. Exner, in Correlation Analysis in Chemistry, Recent Advances, ed. N. B. Chapman and J. Shorter, Plenum Press, New York, 1978, ch. 10 Search PubMed.
  13. (a) I. Lee, C. S. Shim, S. Y. Chung, H. Y. Kim and H. W. Lee, J. Chem. Soc., Perkin Trans. 2, 1988, 1919 RSC; (b) M. R. F. Siggel, A. Streitwieser Jr. and T. D. Thomas, J. Am. Chem. Soc., 1988, 110, 8022 CrossRef CAS.
  14. (a) A. Pross, Adv. Phys. Org. Chem., 1977, 14, 69 CAS; (b) O. Exner, J. Chem. Soc., Perkin Trans. 2, 1993, 973 RSC.
  15. (a) E. A. Castro, F. Ibanez, M. Salas and J. G. Santos, J. Org. Chem., 1991, 56, 4819 CrossRef CAS; (b) B. D. Song and W. P. Jencks, J. Am. Chem. Soc., 1989, 111, 8479 CrossRef CAS.
  16. E. A. Guggenheim, Phil. Mag., 1926, 2, 538 Search PubMed.
Click here to see how this site uses Cookies. View our privacy policy here.