Behavior of N-Chlorosuccinimide Toward Diphenyl Selenide: A Kinetic and Mechanistic Study

K. Sathiyanarayanan; T. Madheswari; Chang Woo Lee

Journal of Industrial and Engineering Chemistry, Vol.13, No.3, 420-423, May, 2007

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Behavior of N-Chlorosuccinimide Toward Diphenyl Selenide: A Kinetic and Mechanistic Study

K. Sathiyanarayanan^†, T. Madheswari, and Chang Woo Lee¹

Department of Chemistry, Vellore Institute of Technology, Vellore - 632 014, India
¹College of Environment & Applied Chemistry, Kyung Hee University, Yongin - 449 701, Korea

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Diphenyl selenide was converted into diphenyl selenoxide using N-chlorosuccinimide in 50 % acetonitrile/water medium under different kinetic conditions and temperatures. The effect of the substrate and oxidant were studied. The order with respect to the concentration of substrate and oxidant was unity. A decrease in polarity of the medium increased the rate of the reaction. Added sodium perchlorate had no effect on the reaction, ruling out the possibility of participation of charged species in the rate-determining step. However, added acrylonitrile decreased the reaction rate considerably, indicating the participation of free radicals during the course of the reaction. Highly negative entropy, ΔS#, indicates a structured transition state. A suitable mechanism in consonance with the observed facts is proposed.

Keywords:kinetics;mechanism;rate law;catalyst;oxidation

[References]

Lonez F, Tetrahedron Lett., 43, 6255 (2002)
Srinivasan NS, Venkatasubramanian N, Tetrahedron, 30, 419 (1974)
Srinivasan NS, Venkatasubramanian N, Tetrahedron Lett., 11, 2039 (1970)
Kuninobu, Nagahara T, Kujoto S, Yamantro Y, Polyhedron, 3, 239 (1984)
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Harville R, Reed SF, J. Org. Chem., 33, 3976 (1968)
Gonzalez-Nunez ME, Mello R, Royo J, Rios JV, Asensio G, J. Am. Chem. Soc., 124(31), 9154 (2002)
Srinivasan C, Kuthalingam P, Arumugam N, Int. J. Chem. Kinet., 14, 1139 (1982)
Gopalakrishnan M, Ph. D. Thesis, Annamalai University (1988)
Srinivasan C, Pitchumani K, Bull. Chem. Soc. Jpn., 55, 289 (1982)
Srinivasan C, Pitchumani K, Indian J. Chem. Sect A-Inorg. Bio-Inorg. Phys. Theor. Anal. Chem., 17A, 162 (1979)
Gurumurthy R, Sathiyanarayanan K, Gopalakrishnan M, Tetrahedron, 50, 13731 (1994)
Gurumurthy R, Anandabaskaran T, Sathiyanarayanan K, Oxidation Commun., 21, 222 (1998)
Sathiyanarayanan K, Pavithra C, Lee CW, J. Ind. Eng. Chem., 12(5), 727 (2006)
Karunakaran K, Elango KP, J. Phys. Org. Chem., 9, 105 (1996)
Srinivasan C, Pitchumani K, Int. J. Chem. Kinet., 14, 789 (1982)
Panigraghi GP, Nayak RN, Curr. Sci., 49, 740 (1980)
Sathiyanarayanan K, Suseela R, Lee CW, J. Ind. Eng. Chem., 12(2), 280 (2006)

[Related Articles]

[1] Lonez F, Tetrahedron Lett., 43, 6255 (2002)

[2] Srinivasan NS, Venkatasubramanian N, Tetrahedron, 30, 419 (1974)

[3] Srinivasan NS, Venkatasubramanian N, Tetrahedron Lett., 11, 2039 (1970)

[4] Kuninobu, Nagahara T, Kujoto S, Yamantro Y, Polyhedron, 3, 239 (1984)

[5] Mathiyalagan N, Sridharan R, Indian J. Chem. Sect A-Inorg. Bio-Inorg. Phys. Theor. Anal. Chem., 44A, 2044 (2005)

[6] Harville R, Reed SF, J. Org. Chem., 33, 3976 (1968)

[7] Gonzalez-Nunez ME, Mello R, Royo J, Rios JV, Asensio G, J. Am. Chem. Soc., 124(31), 9154 (2002)

[8] Srinivasan C, Kuthalingam P, Arumugam N, Int. J. Chem. Kinet., 14, 1139 (1982)

[9] Gopalakrishnan M, Ph. D. Thesis, Annamalai University (1988)

[10] Srinivasan C, Pitchumani K, Bull. Chem. Soc. Jpn., 55, 289 (1982)

[11] Srinivasan C, Pitchumani K, Indian J. Chem. Sect A-Inorg. Bio-Inorg. Phys. Theor. Anal. Chem., 17A, 162 (1979)

[12] Gurumurthy R, Sathiyanarayanan K, Gopalakrishnan M, Tetrahedron, 50, 13731 (1994)

[13] Gurumurthy R, Anandabaskaran T, Sathiyanarayanan K, Oxidation Commun., 21, 222 (1998)

[14] Sathiyanarayanan K, Pavithra C, Lee CW, J. Ind. Eng. Chem., 12(5), 727 (2006)

[15] Karunakaran K, Elango KP, J. Phys. Org. Chem., 9, 105 (1996)

[16] Srinivasan C, Pitchumani K, Int. J. Chem. Kinet., 14, 789 (1982)

[17] Panigraghi GP, Nayak RN, Curr. Sci., 49, 740 (1980)

[18] Sathiyanarayanan K, Suseela R, Lee CW, J. Ind. Eng. Chem., 12(2), 280 (2006)