Bulletin of the Korean Chemical Society

  • 제32권12호
  • /
  • Pages.4361-4365
  • /
  • 2011
  • /
  • 0253-2964(pISSN)
  • /
  • 1229-5949(eISSN)
대한화학회 (Korean Chemical Society)
권호 표지
DOI QR코드

DOI QR Code

Kinetics and Mechanism of the Anilinolysis of Bis(N,N-dimethylamino) Phosphinic Chloride in Acetonitrile

  • 투고 : 2011.10.14
  • 심사 : 2011.10.18
  • 발행 : 2011.12.20
PDF 다운로드
⟨ 이전 논문 다음 논문 ⟩

초록

The nucleophilic substitution reactions of bis(N,N-dimethylamino) phosphinic chloride (3) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at $65.0^{\circ}C$. The anilinolysis rate of 3 is rather slow to be rationalized by the conventional stereoelectronic effects. The magnitudes of ${\rho}_X$ (= -6.42) and ${\beta}_X$ (= 2.27) values are exceptionally great. The deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) are secondary inverse ($k_H/k_D$ = 0.69-0.96). A concerted $S_N2$ mechanism involving a backside attack is proposed on the basis of secondary inverse DKIEs and the variation trend of the $k_H/k_D$ values with X. The anilinolyses of six phosphinic chlorides in MeCN are briefly reviewed by means of DKIEs, steric effects of the two ligands, positive charge of the reaction center phosphorus atom, and selectivity parameters to obtain systematic information on phosphoryl transfer reaction mechanism.

키워드

참고문헌

  1. Guha, A. K.; Lee, H. W.; Lee, I. J. Chem. Soc., Perkin Trans. 2 1999, 765.
  2. Lee, H. W.; Guha, A. K.; Lee, I. Int. J. Chem. Kinet. 2002, 34, 632. https://doi.org/10.1002/kin.10081
  3. Hoque, M. E. U.; Dey, S.; Guha, A. K.; Kim, C. K.; Lee, B. S.; Lee, H. W. J. Org. Chem. 2007, 72, 5493. https://doi.org/10.1021/jo0700934
  4. Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2007, 28, 936. https://doi.org/10.5012/bkcs.2007.28.6.936
  5. Dey, N. K.; Han, I. S.; Lee, H. W. Bull. Korean Chem. Soc. 2007, 28, 2003. https://doi.org/10.5012/bkcs.2007.28.11.2003
  6. Hoque, M. E. U.; Dey, N. K.; Kim, C. K.; Lee, B. S.; Lee, H. W. Org. Biomol. Chem. 2007, 5, 3944. https://doi.org/10.1039/b713167d
  7. Dey, N. K.; Hoque, M. E. U.; Kim, C. K.; Lee, B. S.; Lee, H. W. J. Phys. Org. Chem. 2008, 21, 544. https://doi.org/10.1002/poc.1314
  8. Lumbiny, B. J.; Lee, H. W. Bull. Korean Chem. Soc. 2008, 29, 2065. https://doi.org/10.5012/bkcs.2008.29.10.2065
  9. Dey, N. K.; Hoque, M. E. U.; Kim, C. K.; Lee, B. S.; Lee, H. W. J. Phys. Org. Chem. 2009, 22, 425. https://doi.org/10.1002/poc.1478
  10. Dey, N. K.; Kim, C. K.; Lee, H. W. Bull. Korean Chem. Soc. 2009, 30, 975. https://doi.org/10.5012/bkcs.2009.30.4.975
  11. Hoque, M. E. U.; Guha, A. K.; Kim, C. K.; Lee, B. S.; Lee, H. W. Org. Biomol. Chem. 2009, 7, 2919. https://doi.org/10.1039/b903148k
  12. Dey, N. K.; Lee, H. W. Bull. Korean Chem. Soc. 2010, 31, 1403. https://doi.org/10.5012/bkcs.2010.31.5.1403
  13. Dey, N. K.; Kim, C. K.; Lee, H. W. Org. Biomol. Chem. 2011, 9, 717. https://doi.org/10.1039/c0ob00517g
  14. Barai, H. R.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 1939. https://doi.org/10.5012/bkcs.2011.32.6.1939
  15. Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 1997. https://doi.org/10.5012/bkcs.2011.32.6.1997
  16. Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 2306. https://doi.org/10.5012/bkcs.2011.32.7.2306
  17. Adhikary, K. K.; Lumbiny, B. J.; Dey, S.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 2628. https://doi.org/10.5012/bkcs.2011.32.8.2628
  18. Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 3245. https://doi.org/10.5012/bkcs.2011.32.9.3245
  19. Barai, H. R.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 3355. https://doi.org/10.5012/bkcs.2011.32.9.3355
  20. Taft, R. W. Steric Effect in Organic Chemistry, Newman, M. S., Ed.; Wiley: New York, 1956; Chapter 3.
  21. Exner, O. Correlation Analysis in Chemistry: Recent Advances; Chapman, N. B.; Shorter, J., Eds.; Plenum Press: New York, 1978; p 439.
  22. Hehre, W. J.; Random, L.; Schleyer, P. V. R.; Pople, J. A. Ab Initio Molecular Orbital Theory; Wiley: New York, 1986; Chapter 4.
  23. Hansch, C.; Leo, A.; Taft, R. W. Chem. Rev. 1991, 91, 165. https://doi.org/10.1021/cr00002a004
  24. Streitwieser, A., Jr.; Heathcock, C. H.; Kosower, E. M. Introduction to Organic Chemistry, 4th ed.; Macmillan: New York, 1992; p 735.
  25. Crumpler, T. B.; Yoh, J. H. Chemical Computations and Errors; John Wiley: New York, 1940; p 178.
  26. Ritchie, C. D. in Solute-Solvent Interactions, Coetzee, J. F.; Ritchie, C. D., Ed., Marcel Dekker, New York, 1969; Chapter 4.
  27. Coetzee, J. F. Prog. Phys. Org. Chem. 1967, 4, 54.
  28. Spillane, W. J.; Hogan, G.; McGrath, P.; King, J.; Brack, C. J. Chem. Soc., Perkin Trans. 2 1996, 2099.
  29. Oh, H. K.; Woo, S. Y.; Shin, C. H.; Park, Y. S.; Lee, I. J. Org. Chem. 1997, 62, 5780. https://doi.org/10.1021/jo970413r
  30. Perrin, C. I.; Engler, R. E. J. Phys. Chem. 1991, 95, 8431. https://doi.org/10.1021/j100175a004
  31. Perrin, C. I.; Ohta, B. K.; Kuperman, J. J. Am. Chem. Soc. 2003, 125, 15008. https://doi.org/10.1021/ja038343v
  32. Perrin, C. I.; Ohta, B. K.; Kuperman, J.; Liberman, J.; Erdelyi, M. J. Am. Chem. Soc. 2005, 127, 9641. https://doi.org/10.1021/ja0511927
  33. Poirier, R. A.; Youliang, W.; Westaway, K. C. J. Am. Chem. Soc. 1994, 116, 2526. https://doi.org/10.1021/ja00085a037
  34. Yamata, H.; Ando, T.; Nagase, S.; Hanamusa, M.; Morokuma, K. J. Org. Chem. 1984, 49, 631. https://doi.org/10.1021/jo00178a010
  35. Xhao, X. G.; Tucker, S. C.; Truhlar, D. G. J. Am. Chem. Soc. 1991, 113, 826. https://doi.org/10.1021/ja00003a015
  36. Melander, L. Jr.; Saunders, W. H. Reaction Rates of Isotopic Molecules; Wiley-Interscience: New York, 1980.
  37. Lee, I.; Koh, H. J.; Lee, B. S.; Lee, H. W. J. Chem. Soc., Chem. Commun. 1990, 335.

피인용 문헌

  1. Concerted Pathway to the Mechanism of the Anilinolysis of Bis(N,N-diethylamino)phosphinic Chloride in Acetonitrile vol.70, pp.1, 2017, https://doi.org/10.1071/CH16202
  2. Pyridinolysis of Dibutyl Chlorophosphate in Acetonitrile vol.33, pp.3, 2011, https://doi.org/10.5012/bkcs.2012.33.3.1055
  3. Kinetics and Mechanism of the Anilinolysis of Dibutyl Chlorothiophosphate in Acetonitrile vol.33, pp.3, 2011, https://doi.org/10.5012/bkcs.2012.33.3.843
  4. Kinetics and Mechanism of the Anilinolysis of Dipropyl Chlorophosphate in Acetonitrile vol.33, pp.6, 2012, https://doi.org/10.5012/bkcs.2012.33.6.1879
  5. Anilinolysis of Dimethyl Isothiocyanophosphate in Acetonitrile vol.33, pp.8, 2011, https://doi.org/10.5012/bkcs.2012.33.8.2769