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http://dx.doi.org/10.5012/bkcs.2012.33.6.1879

Kinetics and Mechanism of the Anilinolysis of Dipropyl 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.33, no.6, 2012 , pp. 1879-1884 More about this Journal
Abstract
The kinetic studies on the reactions of dipropyl chlorophosphate (3O) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) have been carried out in acetonitrile at $55.0^{\circ}C$. The obtained deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) are primary normal ($k_H/k_D$ = 1.09-1.01) with the strongly basic anilines while secondary inverse ($k_H/k_D$ = 0.74-0.82) with the weakly basic anilines. The steric effects of the two ligands on the rates are extensively discussed for the anilinolyses of the ($R_1O$)($R_2O$)P(=O or S)Cl-type chlorophosphates and chlorothiophosphates. A concerted mechanism is proposed with a frontside nucleophilic attack involving a hydrogen-bonded four-center-type transition state for the strongly basic anilines and with a backside attack transition state for the weakly basic anilines on the basis of the DKIEs, primary normal and secondary inverse with the strongly and weakly basic anilines, respectively.
Keywords
Phosphoryl transfer reaction; Anilinolysis; Dipropyl chlorophosphate; Deuterium kinetic isotope effect; Steric effect;
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1 Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2012, 33, 663.   DOI   ScienceOn
2 Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2012, 33, 843.   DOI   ScienceOn
3 Taft, R. W. Steric Effect in Organic Chemistry; Newman, M. S., Ed.; Wiley: New York, 1956; Chapter 3.
4 Exner, O. Correlation Analysis in Chemistry: Recent Advances; Chapman, N. B., Shorter, J., Eds.; Plenum Press: New York, 1978; p 439.
5 Hehre, W. J.; Random, L.; Schleyer, P. V. R.; Pople, J. A. Ab Initio Molecular Orbital Theory; Wiley: New York, 1986; Chapter 4.
6 Ritchie, C. D. In Solute-Solvent Interactions; Coetzee, J. F., Ritchie, C. D., Eds.; Marcel Dekker: New York, 1969; Chapter 4.
7 Coetzee, J. F. Prog. Phys. Org. Chem. 1967, 4, 54.
8 Spillane, W. J.; Hogan, G.; McGrath, P.; King, J.; Brack, C. J. Chem. Soc., Perkin Trans. 2 1996, 2099
9 Oh, H. K.; Woo, S. Y.; Shin, C. H.; Park, Y. S.; Lee, I. J. Org. Chem. 1997, 62, 5780.   DOI
10 Perrin, C. I.; Engler, R. E. J. Phys. Chem. 1991, 95, 8431.   DOI
11 Perrin, C. I.; Ohta, B. K.; Kuperman, J. J. Am. Chem. Soc. 2003, 125, 15008.   DOI
12 Perrin, C. I.; Ohta, B. K.; Kuperman, J.; Liberman, J.; Erdelyi, M. J. Am. Chem. Soc. 2005, 127, 9641.   DOI
13 Hansch, C.; Leo, A.; Taft, R. W. Chem. Rev. 1991, 91, 165.   DOI
14 Streitwieser, A., Jr.; Heathcock, C. H.; Kosower, E. M. Introduction to Organic Chemistry, 4th ed.; Macmillan: New York, 1992; p 735.
15 Crumpler, T. B.; Yoh, J. H. Chemical Computations and Errors; John Wiley: New York, 1940; p 178.
16 Lee, I. Chem. Soc. Rev. 1990, 19, 317.   DOI
17 Dey, N. K.; Hoque, M. E. U.; Kim, C. K.; Lee, B. S.; Lee, H. W. J. Phys. Org. Chem. 2009, 22, 425.   DOI
18 Dey, N. K.; Kim, C. K.; Lee, H. W. Bull. Korean Chem. Soc. 2009, 30, 975.   DOI
19 Hoque, M. E. U.; Guha, A. K.; Kim, C. K.; Lee, B. S.; Lee, H. W. Org. Biomol. Chem. 2009, 7, 2919.   DOI
20 Dey, N. K.; Lee, H. W. Bull. Korean Chem. Soc. 2010, 31, 1403.   DOI
21 Dey, N. K.; Kim, C. K.; Lee, H. W. Org. Biomol. Chem. 2011, 9, 717.   DOI
22 Barai, H. R.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 1939.   DOI
23 Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 1997.   DOI
24 Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 2306.   DOI
25 Adhikary, K. K.; Lumbiny, B. J.; Dey, S.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 2628.   DOI
26 Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 3245.   DOI
27 Barai, H. R.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 3355.   DOI
28 Barai, H. R.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 3783.   DOI
29 Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 3880.   DOI
30 Barai, H. R.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 4185.   DOI
31 Barai, H. R.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 4361.   DOI
32 Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 4403.   DOI
33 Guha, A. K.; Lee, H. W.; Lee, I. J. Chem. Soc., Perkin Trans. 2 1999, 765.
34 Lee, H. W.; Guha, A. K.; Lee, I. Int. J. Chem. Kinet. 2002, 34, 632.   DOI
35 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
36 Dey, N. K.; Hoque, M. E. U.; Kim, C. K.; Lee, B. S.; Lee, H. W. J. Phys. Org. Chem. 2008, 21, 544.   DOI
37 Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2007, 28, 936.   DOI
38 Dey, N. K.; Han, I. S.; Lee, H. W. Bull. Korean Chem. Soc. 2007, 28, 2003.   DOI
39 Hoque, M. E. U.; Dey, N. K.; Kim, C. K.; Lee, B. S.; Lee, H. W. Org. Biomol. Chem. 2007, 5, 3944.   DOI
40 Lumbiny, B. J.; Lee, H. W. Bull. Korean Chem. Soc. 2008, 29, 2065.   DOI
41 Gregersen, B. A.; Lopez, X.; York, D. M. J. Am. Chem. Soc. 2003, 125, 7178.   DOI
42 Lee, I.; Lee, H. W. Collect. Czech. Chem. Commun. 1999, 64, 1529.   DOI
43 Hengge, A. C.; Onyido, I. Curr. Org. Chem. 2005, 9, 61.   DOI
44 Omakor, J. E.; Onyido, I.; vanLoon, G. W.; Buncel, E. J. Chem. Soc., Perkin Trans. 2 2001, 324.
45 Hondal, R. J.; Bruzik, K. S.; Zhao, Z.; Tsai, M. D. J. Am. Chem. Soc. 1997, 119, 5477.   DOI
46 Lee, I.; Koh, H. J.; Lee, B. S.; Lee, H. W. J. Chem. Soc., Chem. Commun. 1990, 335.
47 Lee, I. Chem. Soc. Rev. 1995, 24, 223.   DOI
48 Marlier, J. F. Acc. Chem. Res. 2001, 34, 283.   DOI
49 Westaway, K. C. Adv. Phys. Org. Chem. 2006, 41, 217.   DOI
50 Lee, I. Adv. Phys. Org. Chem. 1992, 27, 57.
51 Villano, S. M.; Kato, S.; Bierbaum, V. M. J. Am. Chem. Soc. 2006, 128, 736.   DOI
52 Gronert, S.; Fajin, A. E.; Wong, L. J. Am. Chem. Soc. 2007, 129, 5330.   DOI
53 Poirier, R. A.; Youliang, W.; Westaway, K. C. J. Am. Chem. Soc. 1994, 116, 2526.   DOI
54 Yamata, H.; Ando, T.; Nagase, S.; Hanamusa, M.; Morokuma, K. J. Org. Chem. 1984, 49, 631.   DOI
55 Xhao, X. G.; Tucker, S. C.; Truhlar, D. G. J. Am. Chem. Soc. 1991, 113, 826.   DOI