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Information about Sandmeyer Reaction

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.

The Mechanism of the Sandmeyer Reaction


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] The use of tetrafluoroborate delivers the halide-substituted product, fluorobenzene. Substituting thiols or water for the copper salts generates thioethers or phenols, respectively.

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]:

Enlarge picture
Catalytic Sandmeyer reaction beletskaya 2007

References

1. ^ Traugott Sandmeyer (1884). "Ueber die Ersetzung der Amidgruppe durch Chlor in den aromatischen Substanzen". Berichte der deutschen chemischen Gesellschaft 17 (3): 1633-1635. DOI:10.1002/cber.18840170219. 
2. ^ 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:10.1002/cber.188401702202. 
3. ^ Ludwig Gattermann (1890). "Untersuchungen über Diazoverbindungen". Berichte der deutschen chemischen Gesellschaft 17 (1): 1218-1228. DOI:10.1002/cber.189002301199. 
4. ^ J. K. Kochi (1957). "The Mechanism of the Sandmeyer and Meerwein Reactions". J. Am. Chem. Soc. 79 (11): 2942-2948. DOI:10.1021/ja01568a066. 
5. ^ H. H. Hodgson (1947). "The Sandmeyer Reaction". Chem. Rev. 40 (2): 251-277. DOI:10.1021/cr60126a003. 
6. ^ 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:10.1021/jo00434a017. 
7. ^ Suzuki, N. et al. Perkins Trans. I 1987, 645.
8. ^ Jonathan L. Hartwell (1955). "o-Chlorobromobenzene". Org. Synth.; Coll. Vol. 3: 185.  
9. ^ F. D. Gunstone and S. Horwood Tucker (1963). "1-Chloro-2,6-dinitrobenzene". Org. Synth.; Coll. Vol. 4: 160.  
10. ^ H. T. Clarke and R. R. Read (1941). "o-Tolunitrile and p-Tolunitrile". Org. Synth.; Coll. Vol. 1: 514.  
11. ^ P. Beletskaya, Alexander S. Sigeev, Alexander S. Peregudov, Pavel V. Petrovskii (2007). "Catalytic Sandmeyer Bromination". Synthesis 2007: 2534-2538. DOI:10.1055/s-2007-983784. 
chemical reaction is a process that results in the interconversion of chemical substances.[1] The substance or substances initially involved in a chemical reaction are called reactants.
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aryl refers to any functional group or substituent derived from a simple aromatic ring. There are more specific terms, such as phenyl, to describe unsubstituted aryl groups and subsets of aryl groups (as well as arbitrarily substituted groups: see IUPAC nomenclature), but "aryl" is
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A halide is a binary compound, of which one part is a halogen atom and the other part is an element or radical that is less electronegative than the halogen, to make a fluoride, chloride, bromide, iodide, or astatide compound. Many salts are halides.
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Diazonium compounds or diazonium salts are a group of organic compounds sharing a common functional group with the characteristic structure of R-N2+ X-
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Traugott Sandmeyer

Traugott Sandmeyer
Born September 15 1854
Wettingen, Switzerland
Died March 9 1922 (aged 69)
Zollikon, Switzerland
Residence Germany, Switzerland
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2, 1
(mildly basic oxide)
Electronegativity 1.90 (Pauling scale)
Ionization energies
(more) 1st: 745.5 kJmol−1
2nd: 1957.9 kJmol−1
3rd: 3666 kJmol−1

Atomic radius 135 pm
Atomic radius (calc.
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Copper(I) chloride (quite commonly called cuprous chloride), is the lower chloride of copper, with the formula CuCl. It occurs naturally as the mineral nantokite.
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Radical-nucleophilic aromatic substitution or SRN1 in organic chemistry is a type of substitution reaction in which a certain substituent on an aromatic compound is replaced by a nucleophile through an intermediary free radical species:
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Copper(I) cyanide (CuCN), also copper cyanide, cuprous cyanide, or cupricin (CAS number [ 544-92-3 ], EINECS number 208-883-6) is a white to cream colored or sometimes greenish powdery solid that is insoluble
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Benzonitrile is the chemical compound with the formula C6H5CN, abbreviated PhCN. This aromatic organic compound is colourless, with a sweet almond odour.
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Tetrafluoroborate is the anion BF4−. This tetrahedral species is isoelectronic with many stable and important species including tetrafluomethane, CF4, and the closely related anion perchlorate, ClO4−.
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Fluorobenzene is the chemical compound with the formula C6H5F, often abbreviated PhF. This species is a derivative of benzene, with a single fluorine atom attached. Its major industrial use is as carbon source in the manufacture of steel.
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catalysis is the acceleration (increase in rate) of a chemical reaction by means of a substance called a catalyst, which is itself not consumed by the overall reaction.
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In chemistry, a ligand is an atom, ion, or molecule (see also: functional group) that generally donates one or more of its electrons through a coordinate covalent bond to, or shares its electrons through a covalent bond with, one or more central atoms or ions (these ligands act as
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In chemistry, a ligand is an atom, ion, or molecule (see also: functional group) that generally donates one or more of its electrons through a coordinate covalent bond to, or shares its electrons through a covalent bond with, one or more central atoms or ions (these ligands act as
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Phenanthroline is a heterocyclic organic compound. It can be a ligand in coordination chemistry; in this role it is abbreviated phen. Being a bidentate ligand, it is commonly used as a chelating agent for metal ions.
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A phase transfer catalyst or PTC in chemistry is a type of chemical compound, which facilitates the migration of a particular chemical component in one phase into another phase in a heterogeneous system.
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18-Crown-6 is an organic compound with the formula [C2H4O]6 and the IUPAC name of 1,4,7,10,13,16-hexaoxacyclooctadecane. The compound is a crown ether.
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Traugott Sandmeyer

Traugott Sandmeyer
Born September 15 1854
Wettingen, Switzerland
Died March 9 1922 (aged 69)
Zollikon, Switzerland
Residence Germany, Switzerland
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Chemische Berichte (usually abbreviated as Ber. or Chem. Ber.) is a German-language scientific journal featuring chemistry of all disciplines. Founded in 1868 as
  • Berichte der Deutschen Chemischen Gesellschaft (ISSN 0365-9631, CODEN BDCGAS),

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digital object identifier (or DOI) is a permanent identifier given to a document, which is not related to its current location. A typical use of a DOI is to give a scientific paper or article a unique identifying number that can be used by anyone to locate details of the paper, and
..... Click the link for more information.
Chemische Berichte (usually abbreviated as Ber. or Chem. Ber.) is a German-language scientific journal featuring chemistry of all disciplines. Founded in 1868 as
  • Berichte der Deutschen Chemischen Gesellschaft (ISSN 0365-9631, CODEN BDCGAS),

..... Click the link for more information.
digital object identifier (or DOI) is a permanent identifier given to a document, which is not related to its current location. A typical use of a DOI is to give a scientific paper or article a unique identifying number that can be used by anyone to locate details of the paper, and
..... Click the link for more information.
Chemische Berichte (usually abbreviated as Ber. or Chem. Ber.) is a German-language scientific journal featuring chemistry of all disciplines. Founded in 1868 as
  • Berichte der Deutschen Chemischen Gesellschaft (ISSN 0365-9631, CODEN BDCGAS),

..... Click the link for more information.
digital object identifier (or DOI) is a permanent identifier given to a document, which is not related to its current location. A typical use of a DOI is to give a scientific paper or article a unique identifying number that can be used by anyone to locate details of the paper, and
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Journal of the American Chemical Society (usually abbreviated as J. Am. Chem. Soc., or JACS), is a peer-reviewed scientific journal, published since 1879 by the American Chemical Society.
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digital object identifier (or DOI) is a permanent identifier given to a document, which is not related to its current location. A typical use of a DOI is to give a scientific paper or article a unique identifying number that can be used by anyone to locate details of the paper, and
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Chemical Reviews (usually abbreviated as Chem. Rev.), is a peer-reviewed scientific journal, published since 1900 by the American Chemical Society. As the name indicates, it publishes comprehensive, critical reviews of an area rather than original research.
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digital object identifier (or DOI) is a permanent identifier given to a document, which is not related to its current location. A typical use of a DOI is to give a scientific paper or article a unique identifying number that can be used by anyone to locate details of the paper, and
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Journal of Organic Chemistry (abbreviated as J. Org. Chem. or JOC) is a scientific journal for original contributions of fundamental research in organic and bioorganic chemistry. It is published by the American Chemical Society.
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