Hunsdiecker reaction

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The Hunsdiecker reaction (also called the Borodin reaction after Alexander Borodin) is the organic reaction of silver salts of carboxylic acids with halogens to give organic halides.[1][2][3][4] It is an example of a halogenation reaction. The reaction is named after Heinz Hunsdiecker and Cläre Hunsdiecker.

The Hunsdiecker reaction

Several reviews have been published.[5][6]

Mercuric oxide will also effect this transformation.[7][8]

Reaction mechanism[edit]

The reaction mechanism of the Hunsdiecker reaction is believed to involve organic radical intermediates. The silver salt of the carboxylic acid 1 will quickly react with bromine to form the acyl hypohalite intermediate 2. Formation of the diradical pair 3 allows for radical decarboxylation to form the diradical pair 4, which will quickly recombine to form the desired organic halide 5.

Radicalic mechanism of Hunsdiecker reaction

Variations[edit]

Simonini reaction[edit]

The reaction of silver salts of carboxylic acids with iodine is called the Simonini reaction, named after Angelo Simonini, a student of Adolf Lieben at the University of Vienna. The ratio of the reagents play an important role in the determination of products, namely, if 1:1 ratio of salt and iodine is used alkyl iodide is formed. On the other hand, a 2:1 ratio gives RCOOR. and 3:2 ratio gives both the products.[5][9][10]

The Simonini reaction

See also[edit]

References[edit]

  1. ^ Cläre Hunsdiecker, et al. U.S. Patent # 2,176,181.
  2. ^ Heinz Hunsdiecker; Cläre Hunsdiecker (1942). "Über den Abbau der Salze aliphatischer Säuren durch Brom". Ber. 75 (3): 291–297. doi:10.1002/cber.19420750309. 
  3. ^ Borodin, A. (1861). "Ueber Bromvaleriansäure und Brombuttersäure". Ann. 119: 121–123. doi:10.1002/jlac.18611190113. 
  4. ^ Allen, C. F. H.; Wilson, C. V. (1955), "Methyl 5-bromovalerate", Org. Synth. ; Coll. Vol. 3: 578 
  5. ^ a b Johnson, R. G.; Ingham, R. K. (1956). "The Degradation of Carboxylic Acid Salts by Means of Halogen - the Hunsdiecker Reaction". Chem. Rev. 56 (2): 219–269. doi:10.1021/cr50008a002. 
  6. ^ Wilson, C. V. Org. React. 1957, 9, 341. (Review)
  7. ^ Meek, J. S.; Osuga, D. T. (1973), "Bromocyclopropane", Org. Synth. ; Coll. Vol. 5: 126 
  8. ^ Lampman, G. M.; Aumiller, J. C. (1988), "Mercury(II) oxide-modified Hunsdiecker reaction: 1-Bromo-3-chlorocyclobutane", Org. Synth. ; Coll. Vol. 6: 179 
  9. ^ Simonini, A. (1892). "Über den Abbau der fetten Säuren zu kohlenstoffärmeren Alkoholen". Monatshefte für Chemie 13 (1): 320–325. doi:10.1007/BF01523646. 
  10. ^ Simonini, A. (1893). "Über den Abbau der fetten Säuren zu kohlenstoffärmeren Alkoholen". Monatshefte für Chemie 14 (1): 81–92. doi:10.1007/BF01517859. 

External links[edit]