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http://dx.doi.org/10.5012/bkcs.2012.33.10.3203

Kinetics and Mechanism of the Pyridinolysis of Diisopropyl Chlorothiophosphate 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.10, 2012 , pp. 3203-3207 More about this Journal
Abstract
The nucleophilic substitution reactions of diisopropyl chlorothiophosphate (5) with X-pyridines have been kinetically studied in MeCN at $35.0^{\circ}C$. The Hammett and Br$\ddot{o}$nsted plots for the substituent X variations in the nucleophiles show biphasic concave upwards with a break point at X = 3-Ph. The pyridinolysis rate of 5 exhibits great negative deviation from the Taft plot. A concerted $S_N2$ mechanism is proposed involving a change of the attacking direction of the X-pyridines from a frontside attack with the strongly basic pyridines to a backside attack with the weakly basic pyridines.
Keywords
Thiophosphoryl transfer reaction; Diisopropyl chlorothiophosphate; Pyridinolysis; Biphasic concave upward free energy relationship;
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1 Castro, E. A.; Angel, M.; Campodonico, P.; Santos, J. G. J. Org. Chem. 2002, 67, 8911.   DOI   ScienceOn
2 Castro, E. A.; Pavez, P.; Santos, J. G. J. Org. Chem. 2002, 67, 4494.   DOI   ScienceOn
3 Oh, H. K.; Ku, M. H.; Lee, H. W.; Lee, I. J. Org. Chem. 2002, 67, 3874.   DOI   ScienceOn
4 Castro, E. A.; Pavez, P.; Santos, J. G. J. Org. Chem. 2002, 67, 3129.
5 Castro, E. A.; Pavez, P.; Arellano, D.; Santos, J. G. J. Org. Chem. 2001, 66, 6571.   DOI   ScienceOn
6 Spillane, W. J.; McGrath, P.; Brack, C.; O'Byrne, A. B. J. Org. Chem. 2001, 66, 6313.   DOI   ScienceOn
7 Koh, H. J.; Han, K. L.; Lee, H. W.; Lee, I. J. Org. Chem. 2000, 65, 4706.   DOI   ScienceOn
8 Humeres, E.; Debacher, N. A.; Sierra, M. M. D.; Franco J. D.; Shutz, A. J. Org. Chem. 1998, 63, 1598.   DOI   ScienceOn
9 Baynham, A. S.; Hibbert, F.; Malana, M. A. J. Chem. Soc., Perkin Trans 2 1993, 1711.
10 Oh, H. K.; Ku, M. H.; Lee, H. W.; Lee, I. J. Org. Chem. 2002, 67, 8995.   DOI   ScienceOn
11 Adhikary, K. K.; Lee, H. W.; Lee, I. Bull. Korean Chem. Soc. 2003, 24, 1135.   DOI   ScienceOn
12 Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 2109.   DOI   ScienceOn
13 Barai, H. R.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 2339.   DOI   ScienceOn
14 Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 2805.   DOI   ScienceOn
15 Adhikary, K. K.; Lumbiny, B. J.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 3743.   DOI   ScienceOn
16 Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 4387.   DOI   ScienceOn
17 Ritchie, C. D. Solute Solvent Interactions; Marcel- Dekker: New York, 1969; p 228.
18 Koh, H. J.; Han, K. L.; Lee, H. W.; Lee, I. J. Org. Chem. 1998, 63, 9834.   DOI   ScienceOn
19 Hehre, W. J.; Random, L.; Schleyer, P. V. R.; Pople, J. A. Ab Initio Molecular Orbital Theory; Wiley: New York, 1986; Chapter 4.
20 Lee, I. Chem. Soc. Rev. 1990, 19, 317.   DOI
21 Lee, I. Adv. Phys. Org. Chem. 1992, 27, 57.
22 Lee, I.; Lee, H. W. Collect. Czech. Chem. Commun. 1999, 64, 1529.
23 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
24 Hoque, M. E. U.; Dey, N. K.; Kim, C. K.; Lee, B. S.; Lee, H. W. Org. Biomol. Chem. 2007, 5, 3944.   DOI   ScienceOn
25 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
26 Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 4403.   DOI   ScienceOn
27 Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2012, 33, 843.   DOI   ScienceOn
28 Hoque, M. E. U.; Lee, H. W. unpublished data.
29 Williams, A. Free Energy Relationships in Organic and Bioorganic Chemistry; RSC: Cambridge, UK, 2003; Chapter 7.
30 Ruff, A.; Csizmadia, I. G. Organic Reactions Equilibria, Kinetics and Mechanism; Elsevier: Amsterdam, Netherlands, 1994; Chapter 7.
31 Oh, H. K.; Lee, J. M.; Lee, H. W.; Lee, I. Int. J. Chem. Kinet. 2004, 36, 434.   DOI   ScienceOn
32 Oh, H. K.; Park, J. E.; Lee, H. W. Bull. Korean Chem. Soc. 2004, 25, 1041.   DOI   ScienceOn
33 Dey, N. K.; Hoque, M. E. U.; Kim, C. K.; Lee, H. W. J. Phys. Org. Chem. 2010, 23, 1022.   DOI   ScienceOn
34 Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2012, 33, 325.   DOI   ScienceOn
35 Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2012, 33, 1085.   DOI   ScienceOn
36 Exner, O. Correlation Analysis in Chemistry: Recent Advances; Chapman, N. B., Shorter, J., Eds.; Plenum Press: New York, 1978; p 439.
37 Adhikary, K. K.; Lumbiny, B. J.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 3947.   DOI   ScienceOn
38 Hoque, M. E. U.; Dey, S.; Kim, C. K.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 1138.   DOI   ScienceOn
39 Taft, R. W. Steric Effect in Organic Chemistry; Newman, M. S., Ed.; Wiley: New York, 1956; Chapter 3.
40 Fischer, A.; Galloway, W. J.; Vaughan, J. J. Chem. Soc. 1964, 3591.   DOI
41 Dean, J. A. Handbook of Organic Chemistry; McGraw- Hill: New York, 1987; Chapter 8.
42 Castro, E. A.; Freudenberg, M. J. Org. Chem. 1980, 45, 906.   DOI
43 Lee, I.; Kim, C. K.; Han, I. S.; Lee, H. W.; Kim, W. K.; Kim, Y. B. J. Phys. Chem. B 1999, 103, 7302.   DOI   ScienceOn
44 Coetzee, J. F. Prog. Phys. Org. Chem. 1967, 4, 45.   DOI
45 Spillane, W. J.; Hogan, G.; McGrath, P.; King, J.; Brack, C. J. Chem. Soc., Perkin Trans. 2 1996, 2099.
46 Barai, H. R.; Lee, H. W. Bull. Korean Chem. Soc. 2012, 33, 309.   DOI   ScienceOn