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http://dx.doi.org/10.5012/bkcs.2011.32.9.3245

Kinetics and Mechanism of the Anilinolysis of Diisopropyl Chlorophosphate in Acetonitrile  

Hoque, Md. Ehtesham Ul (Department of Chemistry, Inha University)
Lee, Hai-Whang (Department of Chemistry, Inha University)
Publication Information
Bulletin of the Korean Chemical Society / v.32, no.9, 2011 , pp. 3245-3250 More about this Journal
Abstract
The nucleophilic substitution reactions of diisopropyl chlorophosphate (3) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at $55.0^{\circ}C$. The anilinolysis rate of 3 is rather slow to be rationalized by the conventional stereoelectronic effects. The obtained deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) are secondary inverse ($k_H/k_D$ = 0.71-0.95) with maximum magnitude at X = H.A concerted mechanism involving predominant backside nucleophilic attack is proposed on the basis of the secondary inverse DKIEs.
Keywords
Phosphoryl transfer reaction; Anilinolysis; Diisopropyl chlorophosphate; Deuterium kinetic isotope effect;
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1 Lee, I.; Koh, H. J.; Lee, B. S.; Lee, H. W. J. Chem. Soc., Chem. Commun. 1990, 335.
2 Lee, I. Chem. Soc. Rev. 1995, 24, 223.   DOI
3 Marlier, J. F. Acc. Chem. Res. 2001, 34, 283.   DOI   ScienceOn
4 Westaway, K. C. Adv. Phys. Org. Chem. 2006, 41, 217.   DOI
5 Villano, S. M.; Kato, S.; Bierbaum, V. M. J. Am. Chem. Soc. 2006, 128, 736.   DOI   ScienceOn
6 Gronert, S.; Fajin, A. E.; Wong, L. J. Am. Chem. Soc. 2007, 129, 5330.   DOI   ScienceOn
7 Poirier, R. A.; Youliang, W.; Westaway, K. C. J. Am. Chem. Soc. 1994, 116, 2526.   DOI   ScienceOn
8 Yamata, H.; Ando, T.; Nagase, S.; Hanamusa, M.; Morokuma, K. J. Org. Chem. 1984, 49, 631.   DOI
9 Xhao, X. G.; Tucker, S. C.; Truhlar, D. G. J. Am. Chem. Soc. 1991, 113, 826.   DOI
10 Perrin, C. I.; Ohta, B. K.; Kuperman, J.; Liberman, J.; Erdelyi, M. J. Am. Chem. Soc. 2005, 127, 9641.   DOI   ScienceOn
11 Hansch, C.; Leo, A.; Taft, R. W. Chem. Rev. 1991, 91, 165.   DOI
12 Streitwieser, A., Jr.; Heathcock, C. H.; Kosower, E. M. Introduction to Organic Chemistry, 4th ed.; Macmillan: New York, 1992; p 735.
13 Zeyer, J.; Wasserfallen, A.; Timmis, K. N. App. Environ. Microbiol. 1985, 50, 447.
14 Crumpler, T. B.; Yoh, J. H. Chemical Computations and Errors; John Wiley: New York, 1940; p 178.
15 Hehre, W. J.; Random, L.; Schleyer, P. V. R.; Pople, J. A. Ab Initio Molecular Orbital Theory; Wiley: New York, 1986; Chapter 4.
16 Taft, R. W. Steric Effect in Organic Chemistry; Newman, M. S., Ed.; Wiley: New York, 1956; Chapter 3.
17 Exner, O. Correlation Analysis in Chemistry: Recent Advances; Chapman, N. B., Shorter, J., Eds.; Plenum Press: New York, 1978; p 439.
18 Dunn, E. J.; Buncel, E. Can. J. Chem. 1989, 67, 1440.   DOI
19 Dunn, E. J.; Moir, R. Y.; Buncel, E.; Purdon, J. G.; Bannard, R. A. B. Can. J. Chem. 1990, 68, 1837.   DOI
20 Buncel, E.; Albright, K. G.; Onyido, I. Org. Biomol. Chem. 2004, 2, 601.   DOI   ScienceOn
21 Guha, A. K.; Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 1375.   DOI   ScienceOn
22 Onyido, I.; Albright, K.; Buncel, E. Org. Biomol. Chem. 2005, 3, 1468.   DOI   ScienceOn
23 Williams, A.; Naylor, R. A. J. Chem. Soc. B 1971, 1967.   DOI
24 Douglas, K. T.; Williams, A. J. Chem. Soc., Perkin Trans 2 1976, 515.
25 Guha, A. K.; Kim, C. K.; Lee, H. W. J. Phys. Org. Chem. 2011, 24, 474.   DOI   ScienceOn
26 Adhikary, K. K.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 1945.   DOI   ScienceOn
27 Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 2109.   DOI   ScienceOn
28 Barai, H. R.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 2339.   DOI   ScienceOn
29 Adhikary, K. K.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 1625.   DOI   ScienceOn
30 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.   DOI   ScienceOn
31 Han, I. S.; Kim, C. K.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 889.   DOI   ScienceOn
32 Ritchie, C. D. In Solute-Solvent Interactions, Coetzee, J. F., Ritchie, C. D., Eds.; Marcel Dekker: New York, 1969; Chapter 4.
33 Coetzee, J. F. Prog. Phys. Org. Chem. 1967, 4, 54.
34 Perrin, C. I.; Ohta, B. K.; Kuperman, J. J. Am. Chem. Soc. 2003, 125, 15008.   DOI   ScienceOn
35 Spillane, W. J.; Hogan, G.; McGrath, P.; King, J.; Brack, C. J. Chem. Soc., Perkin Trans. 2 1996, 2099.
36 Oh, H. K.; Woo, S. Y.; Shin, C. H.; Park, Y. S.; Lee, I. J. Org. Chem. 1997, 62, 5780.   DOI   ScienceOn
37 Perrin, C. I.; Engler, R. E. J. Phys. Chem. 1991, 95, 8431.   DOI
38 Dey, N. K.; Kim, C. K.; Lee, H. W. Org. Biomol. Chem. 2011, 9, 717.   DOI   ScienceOn
39 Barai, H. R.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 1939.   DOI   ScienceOn
40 Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 1997.   DOI   ScienceOn
41 Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 2306.   DOI   ScienceOn
42 Guha, A. K.; Lee, H. W.; Lee, I. J. Org. Chem. 2000, 65, 12.   DOI   ScienceOn
43 Lee, H. W.; Guha, A. K.; Kim, C. K.; Lee, I. J. Org. Chem. 2002, 67, 2215.   DOI   ScienceOn
44 Adhikary, K. K.; Lee, H. W.; Lee, I. Bull. Korean Chem. Soc. 2003, 24, 1135.   DOI   ScienceOn
45 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.   DOI   ScienceOn
46 Dey, N. K.; Adhikary, K. K.; Kim, C. K.; Lee, H. W. Bull. Korean Chem. Soc. 2010, 31, 3856.   DOI   ScienceOn
47 Adhikary, K. K.; Lumbiny, B. J.; Kim, C. K.; Lee, H. W. Bull. Korean Chem. Soc. 2008, 29, 851.   DOI   ScienceOn
48 Lumbiny, B. J.; Adhikary, K. K.; Lee, B. S.; Lee, H. W. Bull. Korean Chem. Soc. 2008, 29, 1769.   DOI   ScienceOn
49 Dey, N. K.; Hoque, M. E. U.; Kim, C. K.; Lee, H. W. J. Phys. Org. Chem. 2010, 23, 1022.   DOI   ScienceOn
50 Dey, N. K.; Kim, C. K.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 709.   DOI   ScienceOn
51 Hoque, M. E. U.; Dey, S.; Kim, C. K.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 1138.   DOI   ScienceOn
52 Guha, A. K.; Lee, H. W.; Lee, I. J. Chem. Soc., Perkin Trans. 2 1999, 765.
53 Lee, H. W.; Guha, A. K.; Lee, I. Int. J. Chem. Kinet. 2002, 34, 632.   DOI   ScienceOn
54 Hoque, M. E. U.; Dey, S.; Guha, A. K.; Kim, C. K.; Lee, B. S.; Lee, H. W. J. Org. Chem. 2007, 72, 5493.   DOI   ScienceOn
55 Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2007, 28, 936.   DOI   ScienceOn
56 Lumbiny, B. J.; Lee, H. W. Bull. Korean Chem. Soc. 2008, 29, 2065.   DOI   ScienceOn
57 Dey, N. K.; Han, I. S.; Lee, H. W. Bull. Korean Chem. Soc. 2007, 28, 2003.   DOI   ScienceOn
58 Hoque, M. E. U.; Dey, N. K.; Kim, C. K.; Lee, B. S.; Lee, H. W. Org. Biomol. Chem. 2007, 5, 3944.   DOI   ScienceOn
59 Dey, N. K.; Hoque, M. E. U.; Kim, C. K.; Lee, B. S.; Lee, H. W. J. Phys. Org. Chem. 2008, 21, 544.   DOI   ScienceOn
60 Dey, N. K.; Hoque, M. E. U.; Kim, C. K.; Lee, B. S.; Lee, H. W. J. Phys. Org. Chem. 2009, 22, 425.   DOI   ScienceOn
61 Dey, N. K.; Kim, C. K.; Lee, H. W. Bull. Korean Chem. Soc. 2009, 30, 975.   DOI   ScienceOn
62 Hoque, M. E. U.; Guha, A. K.; Kim, C. K.; Lee, B. S.; Lee, H. W. Org. Biomol. Chem. 2009, 7, 2919.   DOI   ScienceOn
63 Dey, N. K.; Lee, H. W. Bull. Korean Chem. Soc. 2010, 31, 1403.   DOI   ScienceOn