Bucherer reaction

The Bucherer reaction in organic chemistry is the reversible conversion of Naphthol to naphtylamine in presence of ammonia and sodium bisulfite [ H Bucherer. "Journal für Praktische Chemie" 49 (1904) p69] [ H Seeboth. "Angew Chem Int Ed" 6(4) (1967) 307-317 (mechanisme) [http://dx.doi.org/10.1002/anie.196703071 DOI] ] [ R Adams e.a. "Organic Reactions Vol I" (Wiley, 1942)] [ W Pötsch. "Lexikon bedeutender Chemiker" (VEB Bibliographisches Institut Leipzig, 1989)ISBN-13: 978-3323001855 ] [ M B Smith, J March. "March's Advanced Organic Chemistry" (Wiley, 2001) (ISBN 0-471-58589-0)] .

The French chemist R. Lepetit was the first to discover the reaction in 1898 but it was the German chemist Hans Theodor Bucherer (1869-1949) who discovered (independent from Lepetit) its reversibility and its potential in chemistry especially in industry. Bucherer published his results in 1904 and his name is connected to this reaction. The organic reaction also goes by the name Bucherer-Lepetit reaction or (wrongly) the Bucherer-Le Petit reaction.

Mechanism

in the first step of the reaction mechanism a proton adds to a carbon atom with high electron density therefore by preference to C2 or C4 of naphthol (1). This leads to resonance stabilized adducts 1a-1e.

De-aromatization of the first ring of the naphtalene system occurs at the expense of 25 kcal/mol. In the next step a bisulfite anion adds to C3 through 1e. This results in the formation of 3a which tautomerizes to the more stable 3b to the sulfonic acid of tetralone. A nucleophilic addition follows of the amine with formation of 4a and its tautomer 4b loses water to form the resonance stabilized cation 5a. This compound is deprotonated to the imine 5b or the enamine 5c but an equilibrium exists between both species. The enamine eliminates sodium bisulfite with formation of napthylamine 6.

It is important to stress that this is a reversible reaction. The reaction is summarized as follows:

The Bucherer carbazole synthesis is a related reaction.

References