OJSTA  Vol.2 No.1 , January 2013
Competition of Aromatic Bromination and Nitration in Concentrated Sulfuric Acid
ABSTRACT

Composition of bromine and nitric acid in concentrated sulfuric acid is effective for bromination of strongly deactivated aromatic compounds and for nitration and bromination of moderately deactivated compounds in one stage. The question why brominating agent is more reactive than nitrating agent in relation to strongly deactivated aromatic compounds and is less reactive in relation to moderate deactivated ones is discussed.


Cite this paper
A. Andrievsky and M. Gorelik, "Competition of Aromatic Bromination and Nitration in Concentrated Sulfuric Acid," Open Journal of Synthesis Theory and Applications, Vol. 2 No. 1, 2013, pp. 46-50. doi: 10.4236/ojsta.2013.21005.
References
[1]   D. Ioffe and A. Kampf, “Bromine, Organic Compounds,” In: Kirk-Othmer Encyclopedia of Chemical Technology, John Wiley and Sons, Inc., New York, 2007, pp. 340-364.

[2]   A. de Meijere and F. Diederich, “Metal-Catalyzed Cross-Coupling Reactions,” 2nd Edition, Wiley-VCH, Weinheim, 2004.

[3]   S. P. Stanforth, “Vinyl and Aryl Halides,” In: A. R. Katritzky and R. J. K. Taylor, Eds., Comprehensive Organic Functional Group Transformations, Elsevier, Amsterdam, 2005, pp. 561-593.

[4]   A. M. Andrievsky and M. V. Gorelik, “Bromination of Deactivated Aromatic Compounds,” Russian Chemical Reviews, Vol. 80, No. 5, 2011, pp. 421-428. doi:10.1070/RC2011v080n05ABEH004178

[5]   D. H. Derbyshire and W. A. Waters, “The Significance of the Bromine Cation in Aromatic Substitution. Part II. Preparative Applicability,” Journal of the Chemical Society, Vol. 1950, No. 2, 1950, pp. 573-577.

[6]   K. Huthmacher and F. Effenberger, “Neue Reaktive Bromierungsagentinen,” Synthesis, Vol. 1978, No. 9, 1978, pp. 693-694. doi:10.1055/s-1978-24861

[7]   W. Gottardi, “Zur Chemie der Bromisocyanurs?uren: Eigenschaften und Reaktionen der Dibromisocyanurs?ure,” Monatshefte für Chemie—Chemical Monthly, Vol. 108, No. 5, 1977, pp. 1067-1084. doi:10.1007/BF00897688

[8]   S. Rosen and O. Lerman, “Bromination of Deactivated Aromatics Using Bromine Trifluoride without a Catalyst,” The Journal of Organic Chemistry, Vol. 58, No. 1, 1993, pp. 239-240. doi:10.1021/jo00053a043

[9]   A. M. Andrievskii, M. V. Gorelik, S. V. Avidon and E. Sh. Al’tman, “Bromination of Deactivated Aromatic Compounds,” Russian Journal of Organic Chemistry, Vol. 29, No. 9, 1993, pp. 1519-1525.

[10]   L. Kumar, T. Mahajan and D. D. Agarwal, “Bromination of Deactivated Aromatic Compounds with Sodium Bromine/Sodium Periodate under Mild Acidic Conditions,” Industrial & Engineering Chemistry Research, Vol. 51, No. 36, 2012, pp. 11593-11597. doi:10.1021/ie202851k

[11]   M. S. Newman and J. Blum, “4-Bromo- and 4-Iodo-2,5,7-trinitrofluorenones as Complexing Agents,” Journal of the American Chemical Society, Vol. 86, No. 24, 1964, pp. 5600-5602. doi:10.1021/ja01078a039

[12]   D. Hellwinkel and G. Haas, “4,5-Dihalogen-9-Fluorenone,” Justus Liebigs Annalen der Chemie, Vol. 1978, No. 12, 1978, pp. 1913-1915.

[13]   H. O. Jenkins, “The Dipole Moments of Certain Polynitro-Compounds,” Journal of the Chemical Society, No. 6, 1936, pp. 862-867.

[14]   H. Jian and J. M. Tour, “Preparative Fluorous Mixture Synthesis of Diazonium-Functionalized Oligo(Phenylene vinylene)s,” The Journal of Organic Chemistry, Vol. 70, No. 9, 2005, pp. 3396-3424. doi:10.1021/jo048051s

[15]   A. M. Andrievskii, M. V. Gorelik, S. V. Avidon, E. V. Gordievskaya, E. Sh. Al’tman, G. N. Vorozhtsov and K. M. Dyumaev, “Method of Obtaining 2-Bromo-4,6-dinitroaniline,” Chemical Abstracts, Vol. 113, 1990, Article ID: 190886.

[16]   S. Kato, M. Maezawa, S. Hirano and S. Ishigaku, “Nitration of Phenanthraquinone,” Chemical Abstracts, Vol. 51, 1957, Article ID: 10462.

[17]   G. V. Gridunova, Y. T. Struchkov, R. V. Linko, A. M. Andrievskii and B. E. Zaitsev, “X-Ray Structural and Spectral Study of 1:2 Solvate of 2,7-Dinitro-4-bromo-10,10-dihydroxy-9-one with Dimethylformamide,” Bulletin of the Russian Academy of Sciences, Vol. 41, No. 4, 1992, pp. 710-715. doi:10.1007/BF01150897

[18]   D. F. Perepichka, M. R. Bryce, I. F. Perepichka, S. B. Lyubchik, C. A. Christensen, N. Godbert, A. S. Batsanov, E. Levillain, E. J. L. McInnes and J. P. Zhao, “A (π-Extended Tetrathiafulvalene)-Fluorene Conjugate. Unusual Electrochemistry and Charge Transfer Properties:? The First Observation of a Covalent D2+-σ-A?? Redox State,” Journal of the American Chemical Society, Vol. 124, No. 47, 2002, pp. 14227-14238. doi:10.1021/ja012518o

[19]   K. Schofield, “Aromatic Nitration,” Cambridge University Press, Cambridge, 1980.

[20]   L. P. Hammett, “Physical Organic Chemistry,” McGrawHill, New York, 1970.

[21]   C. D. Johnson, “The Hammett Equation,” Cambridge University Press, Cambridge, 1973.

[22]   A. R. Katritzky, S. Clementi and H. O. Tarhan, “Discussion of Standard Nitration Rates for Benzenoid and Heteroaromatic Compounds,” Journal of the Chemical Society, Perkin Transactions 2, Vol. 1975, No. 14, 1975, pp. 1624-1627.

 
 
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