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Kinetics and Mechanism of Oxidation of Aliphatic Secondary Alcohols by Benzyltrimethylammonium Chlorobromate
Corresponding Author(s) : Pradeep K. Sharma
Asian Journal of Chemistry,
Vol. 26 No. 9 (2014): Vol 26 Issue 9
Abstract
Oxidation of several secondary alcohols by benzyltrimethylammonium chlorobromate (BTMACB) in aqueous acetic acid leads to the formation of corresponding ketones. The reaction is first order with respect to BTMACB and the alcohols. The reaction failed to induce the polymerization of acrylonitrile. There is no effect of tetrabutylammonium chloride on the reaction rate. The proposed reactive oxidizing species is chlorobromate ion. The oxidation of benzhydrol-a-d (PhCDOHPh) exhibited a substantial primary kinetic isotope effect (kH/kD = 5.61 at 298 K). The effect of solvent composition indicated that the rate increases with an increase in the polarity of the solvent. The reaction is susceptible to both the polar and steric effects of the substituents. A mechanism involving transfer of a hydride ion in the rate-determining step has been proposed.
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- S. Kajigaeshi, T. Kakinami, M. Moriwaki, S. Fujisaki and T. Okamoto, Tech. Rep. Yamaguchi Univ., 4, 65 (1987).
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References
S. Kajigaeshi, T. Kakinami, M. Moriwaki, S. Fujisaki and T. Okamoto, Tech. Rep. Yamaguchi Univ., 4, 65 (1987).
S. Kajigaeshi, T. Kakinami, H. Yamasaki, S. Fujisaki and T. Okamoto, Bull. Chem. Soc. Jpn., 61, 2681 (1988); doi:10.1246/bcsj.61.2681.
S. Kajigaeshi, T. Kakinami, M. Shimizu, M. Takahashi, S. Fujisaki and T. Okamoto, Tech. Rep. Yamaguchi Univ., 4, 139 (1988).
S. Mitra and K. Sreekumar, Indian J. Chem., 36B, 133 (1997).
V.S. Chouhan and V. Sharma, Int. J. Chem. Sci., 1, 341 (2003).
V.S. Chouhan and V. Sharma, J. Indian Chem. Soc., 82, 302 (2005).
V.S. Chouhan, M. Sharma and V. Sharma, J. Indian Chem. Soc., 84, 582 (2007).
V. Tiwari, A. Meena, A. Daiya, P.T.S.R.K. Prasadrao and V. Sharma, Proc. React. Kinet. Mech., 37, 263 (2012); doi:10.3184/146867812X1330253472635.
M. Baghmar and P.K. Sharma, Int. J. Chem. Kinet., 33, 390 (2001); doi:10.1002/kin.1033.
J. Gosain and P.K. Sharma, J. Indian Chem. Soc., 79, 815 (2002); Proc. Indian Acad. Sci. Chem. Sci., 115, 135 (2003).
P.K. Sharma, J. Indian Chem. Soc., 81, 291 (2004).
N.S. Srinivasan and N. Venkatasubramanian, Tetrahedron, 30, 419 (1974); doi:10.1016/S0040-4020(01)97017-6.
D.D. Perrin, W.L. Armarego and D.R. Perrin, Purification of Organic Compounds, Pergamon; Oxford (1966).
L. Liu and Q.-X. Guo, Chem. Rev., 101, 673 (2001); doi:10.1021/cr990416z.
O. Exner, Collect. Czech. Chem. Commun., 29, 1094 (1964); doi:10.1135/cccc19641094.
V.S.R. Raju, P.K. Sharma and K.K. Banerji, Indian J. Chem., 39A, 650 (2000).
P. Aukett and I.R.L. Barker, J. Chem. Soc., Perkin Trans. 2, 568 (1972); doi:10.1039/p29720000568.
A.H. Fainberg and S. Winstein, J. Am. Chem. Soc., 78, 2770 (1956); doi:10.1021/ja01593a033.
K.B. Wiberg, Physical Organic Chemistry, Wiley, New York; p. 414 (1963).
O. Exner, Prog. Phys. Org. Chem., 10, 411 (1973).
W.A. Pavelich and R.W. Taft Jr., J. Am. Chem. Soc., 79, 4935 (1957); doi:10.1021/ja01575a029.
V.L. Heasley, T.J. Louie, D.K. Luttrull, M.D. Millar, H.B. Moore, D.F. Nogales, A.M. Sauerbrey, A.B. Shevel and T.Y. Shibuya, J. Org. Chem., 53, 2199 (1988); doi:10.1021/jo00245a014.
A. Pareek, S. Varshney and K.K. Banerji, React. Kinet. Catal. Lett., 60, 127 (1997); doi:10.1007/BF02477700.
H. Gangwani, P.K. Sharma and K.K. Banerji, J. Chem. Res., 180 (1999); doi:10.1039/A807200K.
D. Mathur, P.K. Sharma and K.K. Banerji, J. Chem. Soc., Perkin Trans. II, 205 (1993); doi:10.1039/p29930000205.
D. Suri, S. Kothari and K.K. Banerji, J. Chem. Res., (S) 228, (M) 1301 (1996).
E.S. Gould, Mechanism and Structure in Organic Chemistry, Holt, Rinehart and Winston Inc., New York (1964).