NaBr/98% H2SO4: An Efficient Reagent for the Regioselective Monobromination of Least Reactive Alkanes and Cycloalkanes

Authors

  • Pasha Mohamad Afzal Department of Studies in Chemistry, Central College Campus, Bangalore University, Bangalore–560 001
  • Shrivatsa Nagashree Department of Studies in Chemistry, Central College Campus, Bangalore University, Bangalore–560 001

DOI:

https://doi.org/10.12723/mjs.25.1

Keywords:

Monobromination, Acyclic and Cyclic Alkanes, Sodium bromide, 98% H2SO4

Abstract

An efficient, simple and regioselective monobromination of least reactive acyclic and cyclic alkanes by sodium bromide/ 98% H2SO4 is reported. The yields are high and the reactions go to completion within 15–35 min. at                     40–65 ºC.

Author Biographies

Pasha Mohamad Afzal, Department of Studies in Chemistry, Central College Campus, Bangalore University, Bangalore–560 001

Department of Studies in Chemistry,

Shrivatsa Nagashree, Department of Studies in Chemistry, Central College Campus, Bangalore University, Bangalore–560 001

Department of Studies in Chemistry, Central College Campus, Bangalore University, Bangalore–560 001

References

M. Siddiq, S. A. Khan and M. A. Munawar, “Monobromination of deactivated active rings using bromine, mercuric oxide, and strong acid”, J. Org. Chem., vol. 53, pp. 1799-1800, 1988. doi:10.1021/jo00243a037

X. Jiang, M. Shen, Y. Tang and C. Li, “Chemoselective monobromination of alkanes promoted by unactivated MnO2”, Tetrahedron Lett., vol. 46, pp. 487-489, 2005. doi:10.1016/ j.tetlet.2004.11.113

H. Shaw, H. D. Perlmutter, C. Gu, S. D. Acro and T.O. Quibuyen, “Free-radical bromination of selected organic compounds in water”, J. Org. Chem., vol. 62, pp. 236-237, 1997.

A. McKillop, D. Bromley and E. C. Taylor, “Thallium in Organic Synthesis. XXV. Electrophilic Aromatic Bromination Using Bromine and Thallium(III) Acetate 1-3”, J. Org. Chem., vol. 37, pp. 88-92, 1972. doi:10.1021/jo00966a024

R. H. Mitchell, Y. H. Lai and R. V. Williams, "N-Bromosuccinimide-dimethylformamide: a mild, selective nuclear monobromination reagent for reactive aromatic compounds", J. Org. Chem., vol. 44, pp. 4733-4735, 1979. doi:10.1021/jo00393a066

E. S. Huyser, “The Photochemically Induced Reactions of Bromotrichloromethane with Alkyl Aromatics”, J. Am. Chem. Soc., vol. 82, pp. 391-393 , 1960.

I. S. Akhrem, A. V. Orlinkov, L.V. Afanas’eva, E. I. Mysov and M. E. Vol’pin, “Ionic bromination of ethane and other alkanes (cycloalkanes) with bromine catalyzed by the polyhalomethane•2AlBr3 aprotic organic superacids under mild conditions”, Tetrahedron Lett., vol. 36, pp. 9365-9368, 1995. doi:10.1016/0040-4039(95)01986-R

G. A. Olah, A. H. Wu and Farooq, “Synthetic methods and reactions. 137. Ionic chlorination (bromination) of alkanes and cycloalkanes with methylene chloride (bromide)/antimony pentafluoride”, J. Org. Chem., vol. 54, pp. 1463-1465, 1989 . doi:10.1021/jo00267a047

(9a) S. J. Coats and H. H. Wasserman, “The conversion of α-bromo-β-dicarbonyls to vicinal tricarbonyls using dimethyldioxirane and base”, Tetrahedron Lett., vol. 36, pp. 7735-7738, 1995.

(9b) A.V.R. Rao, A. K. Singh, K. M. Reddy and K. Ravikumar, “Regioselective free radical cyclization : a general method for the synthesis of the spiro[4.4]nonane system of fredericamycin A”, J. Chem. Soc., Perkin Trans. 1, pp. 3171-3175, 1993.

(9c) X. Shi, L. Dai, “Halogenation of Stablized Ester Enolates by Cupric Halides”, J. Org. Chem., vol. 58, pp. 4596-4598, 1993.

D. Y. Curtin and C. G. McCarty, “Use of benzophenone N-chlorimine and N-bromimine as halogenating agents”, J. Org. Chem., vol. 32, pp. 223-225, 1967. doi:10.1021/jo01277a058

D. H. R. Barton, S. D. Beviere and W. Chavasiri, “The functionalization of saturated hydrocarbons. Part 25. Ionic substitution reactions in GoAggIV chemistry: the formation of carbon-halogen bonds”, Tetrahedron, vol. 50, pp. 31-46, 1994. doi:10.1016/ S0040-4020(01)80736-5

R. Davis, L. A. Jim, Durrant and C. R. Christopher, “Free radical halogenation of alkanes initiated by transition metal complexes”, J. Organometallic Chem., vol. 316, pp. 147-162, 1986.

Yi. Yi. Myint and M. A. Pasha, “Monohalogenation (bromination and iodination) of electron rich arenes by tetraalkylammonium halides in presence of conc. H2SO4”, Indian J. Chem. vol. 43B, pp. 357-360, 2004.

Yi. Yi. Myint and M. A. Pasha, “Oxidative monobromination of electron-rich arenes by conc. H2SO4 / alkali metal bromides”, J. Chem. Res. (S), vol. 2004, pp. 732-734, 2004.

M. A. Pasha and Yi. Yi. Myint,“Acid-Catalysed Selective Monoiodination of Electron-Rich Arenes by Alkali Metal Iodides”, Synth. Commun., vol. 34, pp. 2829-2833, 2004.

Published

2021-08-27

Issue

Vol. 12 No. 2 (2013): Mapana - Journal of Sciences

Section

Research Articles

License

Copyright (c) 2013 Pasha Mohamad Afzal, Shrivatsa Nagashree

Creative Commons License

This work is licensed under a Creative Commons Attribution-ShareAlike 4.0 International License.