Wolffenstein-Böters reaction

The Wolffenstein-Böters reaction is an organic reaction converting benzene to picric acid by a mixture of aqueous nitric acid and mercury(II) nitrate. [Wolffenstein and Boeters, Chem. Abs., I, 489, 1861 (1908); 4, 369 (1910);] [cite journal
title = Über die katalytische Wirkung des Quecksilbers bei Nitrierungen
author = Richard Wolffenstein, O. Böters
journal = Berichte der deutschen chemischen Gesellschaft
volume = 46
issue = 1
pages = 586-589
year = 1913
url =
doi = 10.1002/cber.19130460177 ] [cite journal
title = Über Nitrierung der Benzoesäure in Gegenwart von Quecksilber
author = R. Wolffenstein, W. Paar
journal = Berichte der deutschen chemischen Gesellschaft
volume = 46
issue = 1
pages = 589-599
year = 1913
url =
doi = 10.1002/cber.19130460178 ]

According to one series of studies the mercury nitrate first takes benzene to the corresponding nitroso compound and through the diazonium salt to the phenol. The presence of nitrite is essential for the reaction; picric acid formation is prevented when urea, a trap for nitrous acid, is added to the mixture. From then on the reaction proceeds as a regular aromatic nitration. ["The Mechanism of the Oxynitration of Benzene" F. H. Westheimer, Edward Segel, and Richard Schramm J. Am. Chem. Soc.; 1947; 69(4) pp 773 - 785; DOI|10.1021/ja01196a011] ["The Oxynitration of Benzene. I. Studies Relating to the Reaction Mechanisms"Marvin Carmack, Manuel M. Baizer, G. Richard Handrick, L. W. Kissinger, and Edward H. Specht J. Am. Chem. Soc.; 1947; 69(4) pp 785 - 790; DOI|10.1021/ja01196a012]

A conceptually related reaction at one time of interest to the pigment industry is the Bohn-Schmidt reaction (1889) involving the hydroxylation of "hydroxyantraquinone" with sulfuric acid and lead or selenium to a polyhydroxylated anthraquinone.

External links

* The Bohn-Schmidt reaction @ Institute of Chemistry, Skopje, Macedonia [http://www.pmf.ukim.edu.mk/PMF/Chemistry/reactions/bohn-schmidt_r_e.htm Link]

References