Oxidative conversion of anilines to azobenzenes with alkaline chloramine-T

Adalagere Somashekar Manjunatha; Shankarlingaiah Dakshayani; Nirmala Vaz; Puttaswamy

Korean Journal of Chemical Engineering, Vol.33, No.2, 697-706, February, 2016

DOI10.1007/s11814-015-0176-x Export Citation

Oxidative conversion of anilines to azobenzenes with alkaline chloramine-T

Adalagere Somashekar Manjunatha, Shankarlingaiah Dakshayani, Nirmala Vaz¹, and Puttaswamy^†

Department of Chemistry, Bangalore University, Central College Campus, Bangalore-560 001, India
¹Department of Chemistry, Jyoti Nivas College Autonomous, Bangalore-560 095, India

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Anilines are widely used in the manufacture of dyes, medicinals, plastics and perfumes. Anilines are readily oxidized to give products depending on reaction conditions. Conversion of anilines to azobenzene is important in organic synthesis. In the course of this research, optimum conditions for the facile oxidative conversion of anilines to azobenzenes have been established in very good yields. The kinetics of oxidation of aniline, p-methoxyaniline, p-methylaniline, p-carboxylicaniline and p-nitroaniline by chloramine-T (CAT) in NaOH medium shows identical kinetics with a first-order dependence of rate on [CAT]o, fractional-order on [Aniline]o, and an inverse-fractional order on [OH.]. Activation parameters and decomposition constants have been determined. Oxidation products were characterized by NMR spectral studies. Isokinetic temperature is 415 K indicating enthalpy as a controlling factor. The rates increased in the order: p-methoxyaniline>p-methylaniline>aniline>p-carboxylicani- line>p-nitroaniline. A Hammett linear free energy relationship is observed for the reaction with ρ=.0.52. Reaction scheme and kinetic rate law were deduced. We have developed a simple and efficient protocol for the synthesis of azobenzenes by anilines in good yields and hence we believe that this methodology will be a valuable addition to the existing methods.

Keywords:Anilines;Chloramine-T;Oxidation-kinetics;Mechanism;Structure Reactivity

[References]

Oxo N, The nitro group in organic synthesis, Wiley-VCH, New York (2001).
Pausacker KH, Scroggie JG, J. Chem. Soc., 4003 (1954)
Kaiser ET, Wiedman SW, J. Am. Chem. Soc., 86, 4354 (1964)
Panigrahi GP, Mahapatro DD, Int. J. Chem. Kinet., 14, 977 (1982)
Reddy MS, Rajanna KC, Naseeruddin A, Int. J. Chem. Kinet., 27, 1143 (1995)
Ramanujam VMS, Trieff NM, J. C. S. Perkin-II, 1275 (1977)
Radhakrishnamurti PS, Rao MDP, Indian J. Chem., 14A, 485 (1975)
Mansoor SS, Shafi SS, Arabian J. Chem., 7, 171 (2014)
Ma HC, Li WF, Lei ZQ, Tetrahedron, 68(39), 8358 (2012)
Radhakrishnamurti PS, Rao MDP, Indian J. Chem., 14(B), 790 (1976)
Panda KA, Mahapatro SN, Panigrahi GP, J. Org. Chem., 46(20), 4000 (1981)
Aguilar CAH, Narayanan J, Singh N, Thangarasu P, J. Phys. Org. Chem., 47(5), 440 (2014)
Zualin Z, James HE, J. Org. Chem., 60, 1326 (1995)
Leal JM, Domingo PL, Garcia B, Ibeas S, New J. Chem., 18(12), 1233 (1994)
Campbell MM, Johnson G, Chem. Rev., 78, 65 (1978)
Bremner DH, Synth. Reagents, 6, 9 (1986)
Banerji KK, Jayaram B, Mahadevappa DS, J. Scient. Industr. Res., 46, 65 (1987)
Puttaswamy, Anuradha TM, Ramachandrappa R, Gowda NMM, Int. J. Chem. Kinet., 32(4), 221 (2000)
Armesto XL, Canle L, Garcia MV, Santaballa JA, J. A. Chem. Soc. Rev., 27, 453 (1998)

[1] Oxo N, The nitro group in organic synthesis, Wiley-VCH, New York (2001).

[2] Pausacker KH, Scroggie JG, J. Chem. Soc., 4003 (1954)

[3] Kaiser ET, Wiedman SW, J. Am. Chem. Soc., 86, 4354 (1964)

[4] Panigrahi GP, Mahapatro DD, Int. J. Chem. Kinet., 14, 977 (1982)

[5] Reddy MS, Rajanna KC, Naseeruddin A, Int. J. Chem. Kinet., 27, 1143 (1995)

[6] Ramanujam VMS, Trieff NM, J. C. S. Perkin-II, 1275 (1977)

[7] Radhakrishnamurti PS, Rao MDP, Indian J. Chem., 14A, 485 (1975)

[8] Mansoor SS, Shafi SS, Arabian J. Chem., 7, 171 (2014)

[9] Ma HC, Li WF, Lei ZQ, Tetrahedron, 68(39), 8358 (2012)

[10] Radhakrishnamurti PS, Rao MDP, Indian J. Chem., 14(B), 790 (1976)

[11] Panda KA, Mahapatro SN, Panigrahi GP, J. Org. Chem., 46(20), 4000 (1981)

[12] Aguilar CAH, Narayanan J, Singh N, Thangarasu P, J. Phys. Org. Chem., 47(5), 440 (2014)

[13] Zualin Z, James HE, J. Org. Chem., 60, 1326 (1995)

[14] Leal JM, Domingo PL, Garcia B, Ibeas S, New J. Chem., 18(12), 1233 (1994)

[15] Campbell MM, Johnson G, Chem. Rev., 78, 65 (1978)

[16] Bremner DH, Synth. Reagents, 6, 9 (1986)

[17] Banerji KK, Jayaram B, Mahadevappa DS, J. Scient. Industr. Res., 46, 65 (1987)

[18] Puttaswamy, Anuradha TM, Ramachandrappa R, Gowda NMM, Int. J. Chem. Kinet., 32(4), 221 (2000)

[19] Armesto XL, Canle L, Garcia MV, Santaballa JA, J. A. Chem. Soc. Rev., 27, 453 (1998)