Browse > Article
http://dx.doi.org/10.5012/bkcs.2014.35.9.2797

Kinetics and Mechanism of Anilinolyses of Aryl Methyl and Aryl Propyl Chlorothiophosphates in Acetonitrile  

Barai, Hasi Rani (Department of Chemistry, Inha University)
Lee, Hai Whang (Department of Chemistry, Inha University)
Publication Information
Bulletin of the Korean Chemical Society / v.35, no.9, 2014 , pp. 2797-2802 More about this Journal
Abstract
Nucleophilic substitution reactions of Y-aryl methyl (8) and Y-aryl propyl (10) chlorothiophosphates with substituted anilines and deuterated anilines are investigated kinetically in acetonitrile at $55.0^{\circ}C$. A concerted mechanism is proposed for 8 based on the negative ${\rho}_{XY}$ (= -0.23) value, while a stepwise mechanism with a rate-limiting leaving group departure from the intermediate is proposed for 10 based on the positive ${\rho}_{XY}$ (= +0.68) value. The deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) are 0.89-1.28 and 0.62-1.20 with 8 and 10, respectively. Primary normal and secondary inverse DKIEs are rationalized by a frontside attack involving hydrogen bonded, four-center-type transition state and backside attack involving in-line-type transition state, respectively.
Keywords
Thiophosphoryl transfer reaction; Anilinolysis; Y-Aryl methyl and Y-aryl propyl chlorothiophosphates; Deuterium kinetic isotope effect; Cross-interaction constant;
Citations & Related Records
Times Cited By KSCI : 12  (Citation Analysis)
연도 인용수 순위
1 (c) Poirier, R. A.; Wang, Y.; Westaway, K. C. J. Am. Chem. Soc. 1994, 116, 2526.   DOI   ScienceOn
2 (a) Barai, H. R.; Lee, H. W. Bull. Korean Chem. Soc. 2014, 35, 753.   DOI
3 (b) Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 3505.   DOI
4 (c) Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2012, 33, 3437.   DOI
5 (d) Barai, H. R.; Lee, H. W. Bull. Korean Chem. Soc. 2013, 34, 3218.   DOI
6 Barai, H. R.; Lee, H. W. Bull. Korean Chem. Soc. 2014, 35, 483.   DOI
7 (d) Lee, I.; Lee, H. W. Bull. Korean Chem. Soc. 2001, 22, 732.
8 (a) Guha, A. K.; Lee, H. W.; Lee, I. J. Chem. Soc., Perkin Trans. 2 1999, 765.
9 (b) Lee, H. W.; Guha, A. K.; Lee, I. Int. J. Chem. Kinet. 2002, 34, 632.   DOI   ScienceOn
10 (c) Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 3245.   DOI
11 (d) Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2012, 33, 663.   DOI   ScienceOn
12 (e) Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2012, 33, 1879.   DOI   ScienceOn
13 (a) Hoque, M. E. U.; Guha, A. K.; Kim, C. K.; Lee, B. S.; Lee, H. W. Org. Biomol. Chem. 2009, 7, 2919.   DOI   ScienceOn
14 (c) Barai, H. R.; Lee, H. W. Beilstein J. Org. Chem. 2013, 9, 615.   DOI   ScienceOn
15 (e) Barai, H. R.; Adhikary, K. K.; Lee, H. W. Bull. Korean Chem. Soc. 2013, 34, 1829.   DOI
16 (a) Lee, I.; Koh, H. J.; Lee, B. S.; Lee, H. W. J. Chem. Soc., Chem. Commun. 1990, 335.
17 (e) Villano, S. M.; Kato, S.; Bierbaum, V. M. J. Am. Chem. Soc. 2006, 128, 736.   DOI   ScienceOn
18 (b) Lee, I. Chem. Soc. Rev. 1995, 24, 223.   DOI   ScienceOn
19 (c) Marlier, J. F. Acc. Chem. Res. 2001, 34, 283.   DOI   ScienceOn
20 (d) Westaway, K. C. Adv. Phys. Org. Chem. 2006, 41, 217.
21 (f) Gronert, S.; Fagin, A. E.; Wong, L. J. Am. Chem. Soc. 2007, 129, 5330.   DOI   ScienceOn
22 (a) Yamata, H.; Ando, T.; Nagase, S.; Hanamura, M.; Morokuma, K. J. Org. Chem. 1984, 49, 631.   DOI
23 (a) 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
24 (b) Barai, H. R.; Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2013, 34, 3811.   DOI
25 (c) Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2011, 32, 4403.   DOI
26 (d) Hoque, M. E. U.; Lee, H. W. Bull. Korean Chem. Soc. 2012, 33, 843.   DOI   ScienceOn
27 (e) Hoque, M. E. U.; Dey, N. K.; Kim, C. K.; Lee, B. S.; Lee, H. W. Org. Biomol. Chem. 2007, 5, 3944.   DOI   ScienceOn
28 (f) 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
29 (a) Taft, R. W. Steric Effect in Organic Chemistry; Newman, M. S., Ed.; Wiley: New York, 1956; Chapter 3.
30 (b) Exner, O. Correlation Analysis in Chemistry: Recent Advances; Chapman, N. B., Shorter, J., Eds.; Plenum Press: New York, 1978; p 439.
31 (a) Lee, I. Chem. Soc. Rev. 1990, 19, 317.   DOI
32 (c) Lee, I.; Lee, H. W. Collect. Czech. Chem. Commun. 1999, 64, 1529.   DOI   ScienceOn
33 (b) Lee, I. Adv. Phys. Org. Chem. 1992, 27, 57.
34 (b) Zhao, X. G.; Tucker, S. C.; Truhlar, D. G. J. Am. Chem. Soc. 1991, 113, 826.   DOI