Kinetics and mechanism of the anilinolysis of dicyclohexyl phosphinic chloride in acetonitrile

Bulletin of the Korean Chemical Society

Volumn 32, Issue 6, 2011, Pages 1997-2002

  Ul Hoque, Md Ehtesham ^a   Lee, Hai Whang ^a  

^a Inha University   (South Korea)

Author keywords

Anilinolysis; Deuterium kinetic isotope effects; Dicyclohexyl phosphinic chloride; Phosphoryl transfer reaction

Indexed keywords

ANILINOLYSIS; DEUTERIUM KINETIC ISOTOPE EFFECT; DEUTERIUM KINETIC ISOTOPE EFFECTS; DICYCLOHEXYL PHOSPHINIC CHLORIDE; ELECTRONIC INFLUENCE; KINETICS AND MECHANISM; NEGATIVE DEVIATIONS; NUCLEOPHILIC SUBSTITUTION REACTIONS; PHOSPHORYL TRANSFER; STEREOELECTRONIC EFFECT; SUBSTITUTED ANILINES; TRANSITION STATE;

ACETONITRILE; ANILINE; CARRIER MOBILITY; CHLORINE COMPOUNDS; DEUTERIUM; SUBSTITUTION REACTIONS;

KINETICS;

EID: 79959409438     PISSN: 02532964     EISSN: 12295949     Source Type: Journal    
DOI: 10.5012/bkcs.2011.32.6.1997     Document Type: Article

References (76)

1. (a) Hudson, R. F. Structure and Mechanism in Organophosphorus Chemistry; Academic Press: London, 1965; Chapter 3.
2. (b) Thatcher, G. R. J.; Kluger, R. Adv. Phys. Org. Chem. 1989, 25, 99.
3. (c) Williams, A. Concerted Organic and Bio-Organic Mechanisms; CRC Press: Boca Raton, 2000; Chapter 7-8.
4. (d) Um, I. H.; Hong, J. Y.; Buncel, E. Chem. Commun. 2001, 27.
5. (e) Um, I. H.; Jeon, S. E.; Baek, M. H.; Park, H. R. Chem. Commun. 2003, 3016.
6. (f) Kirby, A. J.; Lima, M. F.; da Silva, D.; Nome, F. J. Am. Chem. Soc. 2004, 126, 1350.
7. (g) Hengge, A. C. Adv. Phys. Org. Chem. 2005, 40, 49.
8. (h) Kumara Swamy, K. C.; Satish Kumar, N. Acc. Chem. Res. 2006, 39, 324.
9. (i) Um, I. H.; Shin, Y. H.; Han, J. Y.; Mishima, M. J. Org. Chem. 2006, 71, 7715.
10. (j) Um, I. H.; Akhtar, K.; Shin, Y. H.; Han, J. Y. J. Org. Chem. 2007, 72, 3823.
11. (k) Um, I. H.; Park, J. E.; Shin, Y. H. Org. Biomol. Chem. 2007, 5, 3539.
12. (l) Um, I. H.; Shin, Y. H.; Lee, S. E.; Yang, K.; Buncel, E. J. Org. Chem. 2008, 73, 923.
13. (m) Kirby, A. J.; Souza, B. S.; Medeiros, M.; Priebe, J. P.; Manfredi, A. M.; Nome, F. Chem. Commun. 2008, 4428.
14. (n) Um, I. H.; Han, J. Y.; Hwang, S. J. Chem. Eur. J. 2008, 14, 7324.
15. (o) Um, I. H.; Han, J. Y.; Shin, Y. H. J. Org. Chem. 2009, 74, 3073.
16. (a) Lee, I.; Koh, H. J.; Lee, B. S.; Lee, H. W. J. Chem. Soc., Chem. Commun. 1990, 335.
17. (b) Lee, I. Chem. Soc. Rev. 1995, 24, 223.
18. (c) Marlier, J. F. Acc. Chem. Res. 2001, 34, 283.
19. (d) Westaway, K. C. Adv. Phys. Org. Chem. 2006, 41, 217.
20. (e) Villano, S. M.; Kato, S.; Bierbaum, V. M. J. Am. Chem. Soc. 2006, 128, 736.
21. (f) Gronert, S.; Fajin, A. E.; Wong, L. J. Am. Chem. Soc. 2007, 129, 5330.
22. (a) Poirier, R. A.; Youliang, W.; Westaway, K. C. J. Am. Chem. Soc. 1994, 116, 2526.
23. (b) Yamata, H.; Ando, T.; Nagase, S.; Hanamusa, M.; Morokuma, K. J. Org. Chem. 1984, 49, 631.
24. (c) Xhao, X. G.; Tucker, S. C.; Truhlar, D. G. J. Am. Chem. Soc. 1991, 113, 826.
25. (a) Guha, A. K.; Lee, H. W.; Lee, I. J. Chem. Soc., Perkin Trans. 2 1999, 765.
26. (b) Lee, H. W.; Guha, A. K.; Lee, I. Int. J. Chem. Kinet. 2002, 34, 632.
27. (c) Hoque, M. E. U.; Dey, S.; Guha, A. K.; Kim, C. K.; Lee, B. S.; Lee, H. W. J. Org. Chem. 2007, 72, 5493.
28. (d) Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2007, 28, 936.
29. (e) Dey, N. K.; Han, I. S.; Lee, H. W. Bull. Korean Chem. Soc. 2007, 28, 2003.
30. (f) Hoque, M. E. U.; Dey, N. K.; Kim, C. K.; Lee, B. S.; Lee, H. W. Org. Biomol. Chem. 2007, 5, 3944.
31. (g) Dey, N. K.; Hoque, M. E. U.; Kim, C. K.; Lee, B. S.; Lee, H. W. J. Phys. Org. Chem. 2008, 21, 544.
32. (h) Lumbiny, B. J.; Lee, H. W. Bull. Korean Chem. Soc. 2008, 29, 2065.
33. (i) Dey, N. K.; Hoque, M. E. U.; Kim, C. K.; Lee, B. S.; Lee, H. W. J. Phys. Org. Chem. 2009, 22, 425.
34. (j) Dey, N. K.; Kim, C. K.; Lee, H. W. Bull. Korean Chem. Soc. 2009, 30, 975.
35. (k) Hoque, M. E. U.; Guha, A. K.; Kim, C. K.; Lee, B. S.; Lee, H. W. Org. Biomol. Chem. 2009, 7, 2919.
36. (l) Dey, N. K.; Lee, H. W. Bull. Korean Chem. Soc. 2010, 31, 1403.
37. (m) Dey, N. K.; Kim, C. K.; Lee, H. W. Org. Biomol. Chem. 2011, 9, 717.
38. (a) Guha, A. K.; Lee, H. W.; Lee, I. J. Org. Chem. 2000, 65, 12.
39. (b) Lee, H. W.; Guha, A. K.; Kim, C. K.; Lee, I. J. Org. Chem. 2002, 67, 2215.
40. (c) Adhikary, K. K.; Lee, H. W.; Lee, I. Bull. Korean Chem. Soc. 2003, 24, 1135.
41. (d) Hoque, M. E. U.; Dey, N. K.; Guha, A. K.; Kim, C. K.; Lee, B. S.; Lee, H. W. Bull. Korean Chem. Soc. 2007, 28, 1797.
42. (e) Adhikary, K. K.; Lumbiny, B. J.; Kim, C. K.; Lee, H. W. Bull. Korean Chem. Soc. 2008, 29, 851.
43. (f) Lumbiny, B. J.; Adhikary, K. K.; Lee, B. S.; Lee, H. W. Bull. Korean Chem. Soc. 2008, 29, 1769.
44. (g) Dey, N. K.; Hoque, M. E. U.; Kim, C. K.; Lee, H. W. J. Phys. Org. Chem. 2010, 23, 1022.
45. (h) Dey, N. K.; Adhikary, K. K.; Kim, C. K.; Lee, H. W. Bull. Korean Chem. Soc. 2010, 31, 3856.
46. (i) Dey, N. K.; Kim, C. K.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 709.
47. (j) Guha, A. K.; Kim, C. K.; Lee, H. W. J. Phys. Org. Chem. 2011, 24, 474.
48. (a) Lee, I.; Kim, C. K.; Li, H. G.; Sohn, C. K.; Kim, C. K.; Lee, H. W.; Lee, B. S. J. Am. Chem. Soc. 2000, 122, 11162.
49. (b) Han, I. S.; Kim, C. K.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 889.
50. Taft, R. W. Steric Effect in Organic Chemistry, ed.; Newman, M. S.; Wiley: New York, 1956; Chapter 3.
51. Hehre, W. J.; Random, L.; Schleyer, P. V. R.; Pople, J. A. Ab Initio Molecular Orbital Theory; Wiley: New York, 1986; Chapter 4.
52. Comparing the calculation results of MP2/6-311+G(d,p) with those of [B3LYP/6-311+G(d,p)]: NBO charges of P, O, and Cl are 1.881 [1.863], -1.010 [-1.042], and -0.307 [-0.333], respectively, and dihedral angles are 110.3 [112.6], 112.4 [112.2], 113.1 [112.1], and 104.0 [104.6] (see Fig. 1). The calculation results of higher level of MP2/6-311+G(d,p) are similar to those of lower level of B3LYP/6-311+G(d,p).
53. (a) Ritchie, C. D. In Solute-Solvent Interactions, Coetzee, J. F., Ritchie, C. D., Eds.; Marcel Dekker: New York, 1969; Chapter 4.
54. (b) Coetzee, J. F. Prog. Phys. Org. Chem. 1967, 4, 54.
55. (c) Spillane, W. J.; Hogan, G.; McGrath, P.; King, J.; Brack, C. J. Chem. Soc., Perkin Trans. 2 1996, 2099.
56. (d) Oh, H. K.; Woo, S. Y.; Shin, C. H.; Park, Y. S.; Lee, I. J. Org. Chem. 1997, 62, 5780.
57. Perrin and his coworkers reported that the basicities of β-deuterated analogs of benzylamine, N,N-dimethylaniline and methylamine increase roughly by 0.02 pKa units per deuterium, and that these effects are additive; (a) Perrin, C. I.; Engler, R. E. J. Phys. Chem. 1991, 95, 8431.
58. (b) Perrin, C. I.; Ohta, B. K.; Kuperman, J. J. Am. Chem. Soc. 2003, 125, 15008.
59. (c) Perrin, C. I.; Ohta, B. K.; Kuperman, J.; Liberman, J.; Erdelyi, M. J. Am. Chem. Soc. 2005, 127, 9641.
60. (c) Exner, O. Correlation Analysis in Chemistry: Recent Advances; Chapman, N. B., Shorter, J., Eds.; Plenum Press: New York, 1978; p 439.
61. Charton, M. Prog. Phys. Org. Chem. 1987, 16, 287.
62. ≠ = -22 ± 2 eu are obtained
63. (a) Dunn, E. J.; Buncel, E. Can. J. Chem. 1989, 67, 1440.
64. (b) Dunn, E. J.; Moir, R. Y.; Buncel, E.; Purdon, J. G.; Bannard, R. A. B. Can. J. Chem. 1990, 68, 1837.
65. (c) Buncel, E.; Albright, K. G.; Onyido, I. Org. Biomol. Chem. 2004, 2, 601.
66. (d) Onyido, I.; Albright, K.; Buncel, E. Org. Biomol. Chem. 2005, 3, 1468.
67. (a) Williams, A.; Naylor, R. A. J. Chem. Soc. B 1971, 1967.
68. (b) Douglas K. T.; Williams, A. J. Chem. Soc., Perkin Trans 2 1976, 515.
69. Dt = 1.03-1.11 for the reactions of phenylacetyl chlorides with deuterated anilines in MeCN (Lee, H. W.; Lee, J. W.; Koh, H. J.; Lee, I. Bull. Korean Chem. Soc. 1998, 19, 642)
70. Dt = 1.04-1.12 for the reactions of 4-nitrophenyl Nphenylcarbamates with deuterated benzylamines in MeCN (Koh, H. J.; Kim, O. S.; Lee, H. W.; Lee, I. J. Phys. Org. Chem. 1997, 10, 725)
71. Dt = 1.02-1.11 for the reactions of benzhydryl chlorides with deuterated pyrrolidine in MeCN (Chang, S.; Koh, H. J.; Lee, B. S.; Lee, I. J. Org. Chem. 1995, 60, 7760).
72. The obtained order of 1.1 is consistent with the typical value of the secondary normal β-DKIEs. (Lowry, T. H.; Richardson, K. S. Mechanism and Theory in Organic Chemistry, 3rd ed.; Harper and Row: New York, 1987; p 239).
73. (a) Melander, L.; Saunders, W. H., Jr. Reaction Rates of Isotopic Molecules; Wiley: New York, 1981; Chapter 6.
74. (b) Menger, F. M.; Smith, J. H. J. Am. Chem. Soc. 1972, 94, 3824.
75. (a) Buncel, E.; Albright, K.; Onyido, I. Org. Biomol. Chem. 2004, 2, 601.
76. (b) Onyido, I.; Albright, K.; Buncel, E. Org. Biomol. Chem. 2005, 3, 1468.