This MedLibrary.org supplementary page on Sandmeyer reaction is provided directly from the open source Wikipedia as a service to our readers. Please see the note below on authorship of this content, as well as the Wikipedia usage guidelines. To search for other content from our encyclopedia supplement, please use the form below:
Related Sponsors
The Sandmeyer reaction is a chemical reaction used to synthesize aryl halides from aryl diazonium salts.[1][2][3] It is named after the Swiss chemist Traugott Sandmeyer.
.png)
An aromatic (or heterocyclic) amine quickly reacts with a nitrite to form an aryl diazonium salt, which decomposes in the presence of copper(I) salts, such as copper(I) chloride, to form the desired aryl halide.[4][5] The reaction is a radical-nucleophilic aromatic substitution.
Several improvements have been made to the standard procedures.[6][7]
Variations
The majority of variations of the Sandmeyer reactions consist of using various copper salts.[8][9] For example, using cuprous cyanide produces benzonitriles.[10] Substituting thiols or water for the copper salts generates thioethers or phenols, respectively.
The Schiemann reaction uses tetrafluoroborate and delivers the halide-substituted product, fluorobenzene, which is not obtained by the use of copper fluorides.
Sandmeyer reactions with copper salts used in catalytic amounts are also known. One bromination protocol employs a 0.2 equivalent Cu(I)/Cu(II) mixture with additional amounts of the bidentate ligand phenanthroline and phase-transfer catalyst dibenzo-18-crown-6 [11]:
References
- ^ Traugott Sandmeyer (1884). "Ueber die Ersetzung der Amidgruppe durch Chlor in den aromatischen Substanzen". Berichte der deutschen chemischen Gesellschaft 17 (3): 1633–1635. doi:.
- ^ Traugott Sandmeyer (1884). "Ueber die Ersetzung der Amid-gruppe durch Chlor, Brom und Cyan in den aromatischen Substanzen". Berichte der deutschen chemischen Gesellschaft 17 (4): 2650–2653. doi:.
- ^ Ludwig Gattermann (1890). "Untersuchungen über Diazoverbindungen". Berichte der deutschen chemischen Gesellschaft 17 (1): 1218–1228. doi:.
- ^ J. K. Kochi (1957). "The Mechanism of the Sandmeyer and Meerwein Reactions". J. Am. Chem. Soc. 79 (11): 2942–2948. doi:.
- ^ H. H. Hodgson (1947). "The Sandmeyer Reaction". Chem. Rev. 40 (2): 251–277. doi:.
- ^ M. P. Doyle, B. Siegfried and J. F. Dellaria (1977). "Alkyl nitrite-metal halide deamination reactions. 2. Substitutive deamination of arylamines by alkyl nitrites and copper(II) halides. A direct and remarkably efficient conversion of arylamines to aryl halides". J. Org. Chem. 42 (14): 2426–2431. doi:.
- ^ Suzuki, N. et al. Perkins Trans. I 1987, 645.
- ^ Jonathan L. Hartwell (1955). "o-Chlorobromobenzene". Org. Synth.; Coll. Vol. 3: 185.
- ^ F. D. Gunstone and S. Horwood Tucker (1963). "1-Chloro-2,6-dinitrobenzene". Org. Synth.; Coll. Vol. 4: 160.
- ^ H. T. Clarke and R. R. Read (1941). "o-Tolunitrile and p-Tolunitrile". Org. Synth.; Coll. Vol. 1: 514.
- ^ P. Beletskaya, Alexander S. Sigeev, Alexander S. Peregudov, Pavel V. Petrovskii (2007). "Catalytic Sandmeyer Bromination". Synthesis 2007: 2534–2538. doi:.
Wikipedia content modification information:
- This page was last modified on 4 September 2008, at 16:41.
Wikipedia Authorship and Review
Wikipedia content provided here is not reviewed directly by MedLibrary.org. Wikipedia content is authored by an open community of volunteers and is not produced by or in any way affiliated with MedLibrary.org.
Wikipedia Usage Guidelines
This article is licensed under the GNU Free Documentation License. It uses material from the Wikipedia article on "Sandmeyer reaction".
The URL for this specific entry is:
All Wikipedia text is available under the terms of the GNU Free Documentation License. (See Copyrights for details). Wikipedia® is a registered trademark of the Wikimedia Foundation, Inc.