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Bamberger Rearrangement

The Bamberger rearrangement is a chemical reaction where N-phenylhydroxylamines rearrange to form 4-aminophenols when reacted with strong aqueous acid. N-phenylhydroxylamines are typically synthesized from nitrobenzenes using rhodium or zinc reduction. The reaction mechanism proceeds through O-protonation of N-phenylhydroxylamine, forming a nitrenium ion intermediate that reacts with water to form the 4-aminophenol product.

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2K views2 pages

Bamberger Rearrangement

The Bamberger rearrangement is a chemical reaction where N-phenylhydroxylamines rearrange to form 4-aminophenols when reacted with strong aqueous acid. N-phenylhydroxylamines are typically synthesized from nitrobenzenes using rhodium or zinc reduction. The reaction mechanism proceeds through O-protonation of N-phenylhydroxylamine, forming a nitrenium ion intermediate that reacts with water to form the 4-aminophenol product.

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John Espique
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The Bamberger rearrangement is the chemical reaction of N-phenylhydroxylamines with strong

aqueous acid, which will rearrange to give 4-aminophenols.[1][2][3] It is named for the German
chemist Eugen Bamberger (18571932).

N-Phenylhydroxylamines are typically synthesized from nitrobenzenes by reduction using


rhodium[4] or zinc.[5]

Reaction mechanism
The mechanism of the Bamberger rearrangement proceeds from the monoprotonation of Nphenylhydroxylamine 1. N-protonation 2 is favored, but unproductive. O-protonation 3 can form the
nitrenium ion 4, which can react with nucleophiles (H2O) to form the desired 4-aminophenol 5.[6][7]

References

1. ^ Bamberger, E. (1894). "Ueber die Reduction der Nitroverbindungen" . Chemische Berichte 27


(2): 13471350. doi:10.1002/cber.18940270229 .
2. ^ Bamberger, E. (1894). "Ueber das Phenylhydroxylamin" . Chemische Berichte 27 (2): 1548
1557. doi:10.1002/cber.18940270276 .
3. ^ Harman, R. E. (1955). "Chloro-p-benzoquinone"

(PDF). Org. Synth. 35: 22.; Coll. Vol. 4, p.148

4. ^ Oxley, P. W.; Adger, B. M.; Sasse, M. J.; Forth, M. A. (1989). "N-Acetyl-N-phenylhydroxylamine


via Catalytic Transfer Hydrogenation of Nitrobenzene using Hydrazine and Rhodium on Carbon"
(PDF). Org. Synth. 67: 187.; Coll. Vol. 8, p.16

5. ^ Kamm, O. (1925). "-Phenylhydroxylamine" . Org. Synth. 4: 57.; Coll. Vol. 1, p.445 (download
PDF ).
6. ^ Sone, T.; Hamamoto, K.; Seiji, Y.; Shinkai, S.; Manabe, O. (1981). "Kinetics and Mechanisms of
the Bamberger Rearrangement. Part 4. Rearrangement of Sterically Hindered
Phenylhydroxylamines to 4-Aminophenols in Aqueous Sulphuric Acid Solution". Journal of the
Chemical Society-Perkin Transactions II 1981 (2): 15961598. doi:10.1039/P29810000298 .
7. ^ Kohnstam, G.; Petch, W. A.; Williams, D. L. H. (1984). "Kinetic Substituent and Isotope Effects in
the Acid-Catalysed Rearrangement of N-Phenylhydroxylamines. Are Nitrenium Ions Involved?".
Journal of the Chemical Society-Perkin Transactions II 1984 (3): 423427.
doi:10.1039/P29840000423 .

See also
FriedelCrafts alkylation-like reactions:
Hofmann-Martius rearrangement
Fries rearrangement
FischerHepp rearrangement

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