Browse > Article
http://dx.doi.org/10.5012/bkcs.2011.32.11.3880

Kinetics and Mechanism of the Anilinolysis of Diisopropyl Thiophosphinic Chloride in Acetonitrile  

Ul Hoque, Md. Ehtesham (Department of Chemistry, Inha University)
Lee, Hai-Whang (Department of Chemistry, Inha University)
Publication Information
Bulletin of the Korean Chemical Society / v.32, no.11, 2011 , pp. 3880-3886 More about this Journal
Abstract
The nucleophilic substitution reactions of diisopropyl thiophophinic 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 obtained deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) are secondary inverse ($k_H/k_D$ = 0.80-0.96). The anilinolyses of ten P=S systems in MeCN are reviewed on the basis of DKIEs and selectivity parameters to obtain systematic information on the DKIEs and mechanism for thiophosphoryl transfer reactions. The steric effects of the two ligands on reactivity, DKIEs, mechanism, and substituent effects of the nucleophile (X) on the DKIEs are discussed.
Keywords
Phosphoryl transfer reaction; Anilinolysis; Diisopropyl thiophosphinic chloride; Deuterium kinetic isotope effect;
Citations & Related Records
Times Cited By KSCI : 23  (Citation Analysis)
Times Cited By Web Of Science : 6  (Related Records In Web of Science)
Times Cited By SCOPUS : 8
연도 인용수 순위
1 Poirier, R. A.; Youliang, W.; Westaway, K. C. J. Am. Chem. Soc. 1994, 116, 2526.   DOI   ScienceOn
2 Yamata, H.; Ando, T.; Nagase, S.; Hanamusa, M.; Morokuma, K. J. Org. Chem. 1984, 49, 631.   DOI
3 Xhao, X. G.; Tucker, S. C.; Truhlar, D. G. J. Am. Chem. Soc. 1991, 113, 826.   DOI
4 Melander, L., Jr.; Saunders, W. H. Reaction Rates of Isotopic Molecules; Wiley-Interscience: New York, 1980.
5 Lee, I.; Koh, H. J.; Lee, B. S.; Lee, H. W. J. Chem. Soc., Chem. Commun. 1990, 335.
6 Lee, I. Chem. Soc. Rev. 1990, 19, 317.   DOI
7 Lee, I. Adv. Phys. Org. Chem. 1992, 27, 57.
8 Lee, I.; Lee, H. W. Collect. Czech. Chem. Commun. 1999, 64, 1529.   DOI   ScienceOn
9 Hehre, W. J.; Random, L.; Schleyer, P. V. R.; Pople, J. A. Ab Initio Molecular Orbital Theory; Wiley: New York, 1986; Chapter 4.
10 Ritchie, C. D. In Solute-Solvent Interactions; Coetzee, J. F., Ritchie, C. D., Eds.; Marcel Dekker: New York, 1969; Chapter 4.
11 Coetzee, J. F. Prog. Phys. Org. Chem. 1967, 4, 54.
12 Spillane, W. J.; Hogan, G.; McGrath, P.; King, J.; Brack, C. J. Chem. Soc., Perkin Trans. 2 1996, 2099.
13 Oh, H. K.; Woo, S. Y.; Shin, C. H.; Park, Y. S.; Lee, I. J. Org. Chem. 1997, 62, 5780.   DOI   ScienceOn
14 Perrin, C. I.; Engler, R. E. J. Phys. Chem. 1991, 95, 8431.   DOI
15 Perrin, C. I.; Ohta, B. K.; Kuperman, J. J. Am. Chem. Soc. 2003, 125, 15008.   DOI   ScienceOn
16 Perrin, C. I.; Ohta, B. K.; Kuperman, J.; Liberman, J.; Erdelyi, M. J. Am. Chem. Soc. 2005, 127, 9641.   DOI   ScienceOn
17 Hansch, C.; Leo, A.; Taft, R. W. Chem. Rev. 1991, 91, 165.   DOI
18 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
19 Adhikary, K. K.; Lumbiny, B. J.; Kim, C. K.; Lee, H. W. Bull. Korean Chem. Soc. 2008, 29, 851.   DOI   ScienceOn
20 Lumbiny, B. J.; Adhikary, K. K.; Lee, B. S.; Lee, H. W. Bull. Korean Chem. Soc. 2008, 29, 1769.   DOI   ScienceOn
21 Guha, A. K.; Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 1375.   DOI   ScienceOn
22 Dey, N. K.; Adhikary, K. K.; Kim, C. K.; Lee, H. W. Bull. Korean Chem. Soc. 2010, 31, 3856.   DOI   ScienceOn
23 Dey, N. K.; Kim, C. K.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 709.   DOI   ScienceOn
24 Hoque, M. E. U.; Dey, S.; Kim, C. K.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 1138.   DOI   ScienceOn
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 Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 2805.   DOI   ScienceOn
30 Adhikary, K. K.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 1625.   DOI   ScienceOn
31 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
32 Han, I. S.; Kim, C. K.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 889.   DOI   ScienceOn
33 Dey, N. K.; Han, I. S.; Lee, H. W. Bull. Korean Chem. Soc. 2007, 28, 2003.   DOI   ScienceOn
34 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
35 Hoque, M. E. U.; Dey, N. K.; Kim, C. K.; Lee, B. S.; Lee, H. W. Org. Biomol. Chem. 2007, 5, 3944.   DOI   ScienceOn
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   ScienceOn
37 Lumbiny, B. J.; Lee, H. W. Bull. Korean Chem. Soc. 2008, 29, 2065.   DOI   ScienceOn
38 Dey, N. K.; Kim, C. K.; Lee, H. W. Bull. Korean Chem. Soc. 2009, 30, 975.   DOI   ScienceOn
39 Hoque, M. E. U.; Guha, A. K.; Kim, C. K.; Lee, B. S.; Lee, H. W. Org. Biomol. Chem. 2009, 7, 2919.   DOI   ScienceOn
40 Dey, N. K.; Lee, H. W. Bull. Korean Chem. Soc. 2010, 31, 1403.   DOI   ScienceOn
41 Dey, N. K.; Kim, C. K.; Lee, H. W. Org. Biomol. Chem. 2011, 9, 717.   DOI   ScienceOn
42 Barai, H. R.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 1939.   DOI   ScienceOn
43 Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 1997.   DOI   ScienceOn
44 Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 2306.   DOI   ScienceOn
45 Adhikary, K. K.; Lumbiny, B. J.; Dey, S.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 2628.   DOI   ScienceOn
46 Guha, A. K.; Lee, H. W.; Lee, I. J. Org. Chem. 2000, 65, 12.   DOI   ScienceOn
47 Lee, H. W.; Guha, A. K.; Kim, C. K.; Lee, I. J. Org. Chem. 2002, 67, 2215.   DOI   ScienceOn
48 Guha, A. K.; Lee, H. W.; Lee, I. J. Chem. Soc., Perkin Trans. 2 1999, 765.
49 Adhikary, K. K.; Lee, H. W.; Lee, I. Bull. Korean Chem. Soc. 2003, 24, 1135.   DOI   ScienceOn
50 Dey, N. K.; Hoque, M. E. U.; Kim, C. K.; Lee, H. W. J. Phys. Org. Chem. 2010, 23, 1022.   DOI   ScienceOn
51 Lee, H. W.; Guha, A. K.; Lee, I. Int. J. Chem. Kinet. 2002, 34, 632.   DOI   ScienceOn
52 Streitwieser, A., Jr.; Heathcock, C. H.; Kosower, E. M. Introduction to Organic Chemistry, 4th ed.; Macmillan: New York, 1992; p 735.
53 Crumpler, T. B.; Yoh, J. H. Chemical Computations and Errors; John Wiley: New York, 1940; p 178.
54 More O'Ferrall, R. A. J. Chem. Soc. B 1970, 274.   DOI
55 Jencks, W. P. Chem. Rev. 1972, 72, 705.   DOI
56 Birdsall, D. J.; Slawin, A. M. Z.; Woollins, J. D. Polyhedron 2001, 20, 125.   DOI   ScienceOn
57 Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2007, 28, 936.   DOI   ScienceOn
58 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