ESTONIAN ACADEMY
PUBLISHERS
eesti teaduste
akadeemia kirjastus
PUBLISHED
SINCE 1952
 
Proceeding cover
proceedings
of the estonian academy of sciences
ISSN 1736-7530 (Electronic)
ISSN 1736-6046 (Print)
Impact Factor (2022): 0.9
Solvent-free synthesis of molecular bromine and its application for in situ bromination of aromatic compounds; pp. 208–214
PDF | 10.3176/proc.2020.3.04

Authors
Ida Rahu, Jaak Järv
Abstract

Synthesis of molecular bromine in solvent-free reaction was studied using two different reaction mixtures. The first mixture consisted of solid KNO3 and gaseous HBr, while the second setup used solid NaBr, KNO3 and gaseous HCl. Bromine formation was determined through bromination reaction of acetanilide, added into the reaction mixture, and monitored by the gas chromatography–mass spectrometry (GC–MS). It was found that this solvent-free oxidative bromination technique could also be used for bromination of several other activated aromatic compounds but bromination of deactivated aromatics under the same condition was not successful, pointing to the need for a catalyst. The developed solvent-free bromination method for aromatics has several benefits as there is no need for heating, the oxidizing agent is mild, and product purification procedure is simple. All mentioned features make this process quite perspective for synthetic applications.

References

1. Nath, J. and Chaudhuri, M. K. Boric acid catalyzed bromination of a variety of Organic Substrates: an eco-friendly and practical protocol. Green Chem. Lett. Rev., 2008, 1(4), 223–230.
https://doi.org/10.1080/17518250902758887

2. Podgoršek, A., Stavber, S., Zupan, M., and Iskra, J. Environmentally benign electrophilic and radical bromination ‘on water’: H2O2–HBr system versus N-bromosuccinimide. Tetrahedron, 2009, 65(22), 4429–4439.
https://doi.org/10.1016/j.tet.2009.03.034

3. Menini, L., Parreira, L. A., and Gusevskaya, E. V. A practical highly selective oxybromination of phenols with dioxygen. Tetrahedron Lett., 2007, 48(36), 6401–6404.
https://doi.org/10.1016/j.tetlet.2007.06.093

4. Zhang, G., Liu, R., Xu, Q., Ma, L., and Liang, X. Sodium nitrite-catalyzed oxybromination of aromatic compounds and aryl ketones with a combination of hydrobromic acid and molecular oxygen under mild conditions. Adv. Synth. Catal., 2006, 348(7–8), 862–866.
https://doi.org/10.1002/adsc.200505495

5. Medina, I. C. R. and Hanson, J. R. The oxidative bromination and iodination of dimethylacetanilides. J. Chem. Res., 2003, 2003(7), 428–429.
https://doi.org/10.3184/030823403103174399

6. Dewkar, G. K., Narina, S. V., and Sudalai, A. NaIO4-mediated selective oxidative halogenation of alkenes and aromatics using alkali metal halides. Org. Lett., 2003, 5(23), 4501–4504.
https://doi.org/10.1021/ol0358206

7. Kim, E.-H., Koo, B.-S., Song, C.-E., and Lee, K.-J. Halogenation of aromatic methyl ketones using Oxone® and sodium halide. Synth. Commun., 2001, 31(23), 3627–3632.
https://doi.org/10.1081/SCC-100107011

8. Petzold, D. and König, B. Photocatalytic oxidative bromination of electron-rich arenes and heteroarenes by anthraquinone. Adv. Synth. Catal., 2018, 360(4), 626–630.
https://doi.org/10.1002/adsc.201701276

9. Mestres, R. and Palenzuela, J. High atomic yield bromine-less benzylic bromination. Green Chem., 2002, 4, 314–316.
https://doi.org/10.1039/b203055a

10. Bard, A. J., Parsons, R., and Jordan, J. Standard Potentials in Aqueous Solution. CRC Press, New York, 1985.

11. Kavala, V., Naik, S., and Patel, B. K. A new recyclable ditribromide reagent for efficient bromination under solvent free condition. J. Org. Chem., 2005, 70(11), 4267–4271.
https://doi.org/10.1021/jo050059u

12. Alimenla, B., Bernandette, K., and Upsana, B. S. Tetrapropylammonium tribromide – an efficient reagent for solvent-free brominations. Chem. Sci. Trans., 2014, 3(2), 826–832.

13. Borikar, S. P. and Daniel, T. Aromatic bromination of aldehydes and ketones using 1,3-di-n-butylimidazolium tribromide [BBIm]Br3 ionic liquids under solvent-free conditions. J. Iran. Chem. Soc., 2011, 8, 531–536.
https://doi.org/10.1007/BF03249087

14. Le, Z.-G., Chen, Z.-C., and Hu, Y. (Bmim)Br3 as a new reagent for regioselective monobromination of phenols and several activated aromatics under solvent-free conditions. Chin. J. Chem., 2005, 23(11), 1537–1540.
https://doi.org/10.1002/cjoc.200591537

15. Chakradhar, A., Roopa, R., Rajanna, K. C., and Saiprakash, P. K. Vilsmeier–Haack bromination of aromatic compounds with KBr and N-bromosuccinimide under solvent-free conditions. Synth. Commun., 2009, 39(10), 1817–1824.
https://doi.org/10.1080/00397910802594268

16. Imanzadeh, G. K., Zamanloo, M. R., Eskandari, H., and Shayesteh, K. A New Ring Bromination Method for Aromatic Compounds under Solvent-Free Conditions with Nbs/Al2O3J. Chem. Res., 2006, 2006(3), 151–153.
https://doi.org/10.3184/030823406776330657

17. Ghorbani-Vaghei, R., Shahbazi, H., and Veisi, H. Mild bromi­nation of unreactive aromatic compounds. Tetrahedron Lett., 2012, 53(18), 2325–2327.
https://doi.org/10.1016/j.tetlet.2012.02.101

18. Wang, G.-W. and Gao, J. Solvent-free bromination reactions with sodium bromide and oxone promoted by mechanical milling. Green Chem., 2012, 14, 1125–1131.
https://doi.org/10.1039/c2gc16606b

19. Anastas, P. T. and Warner, J. C. Green Chemistry: Theory and Practice. Oxford University Press, Oxford, 2000.

20. Lide, D. R. CRC Handbook of Chemistry and Physics90th Edition. CRC Press, Boca Raton, USA, 2009.

21. Atkins, P. W., Overton, T. L., Rourke, J. P., Weller, M. T., and Armstrong, F. A. Shriver and Atkins’ Inorganic Chemistry, 5th Edition. Oxford University Press, Oxford, 2010.

22. Rahu, I., Kekišev, O., Järv, J., and Burk, P. Bromine formation in solid NaBr/KNO3 mixture and assay of this reaction via bromination of activated aromatics. Chem. Pap., 2018, 72, 2893–2898. 
https://doi.org/10.1007/s11696-018-0526-3

23. Harrison, L. G. and Siddiqui, R. A. Reaction of hydrogen chloride gas with sodium bromide; a study in surface thermodynamics. Trans. Faraday Soc., 1962, 58, 982–996.
https://doi.org/10.1039/tf9625800982

Back to Issue