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Reimer–Tiemann Reaction

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118 views3 pages

Reimer–Tiemann Reaction

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kumarsuresh17709
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Reimer–Tiemann reaction

The Reimer–Tiemann reaction is a chemical Reimer–Tiemann reaction


reaction used for the ortho-formylation of also known as RT reaction
phenols; [1][2][3][4][5] with the simplest example being
Named Karl Reimer
the conversion of phenol to salicylaldehyde. The
reaction was discovered by Karl Reimer[6] and after Ferdinand
Ferdinand Tiemann. The Reimer in question was Karl Tiemann
Reimer (1845-1883) not the less known Carl Ludwig Reaction Substitution
Reimer (1856-1921).[7] type reaction
Identifiers
RSC RXNO:0000072
ontology ID

Contents
Reaction mechanism
Selectivity
Reaction conditions
Scope
Comparison to other methods
Variations
References

Reaction mechanism
Chloroform (1) is deprotonated by a strong base (normally hydroxide) to form the
chloroform carbanion (2) which will quickly alpha-eliminate to give dichlorocarbene
(3); this is the principal reactive species. The hydroxide will also deprotonate the
phenol (4) to give a negatively charged phenoxide (5). The negative charge is
delocalised into the aromatic ring, making it far more nucleophilic. Nucleophilic
attack of the dichlorocarbene gives an intermediate dichloromethyl substituted
phenol (7). After basic hydrolysis, the desired product (9) is formed.[8]

Selectivity

By virtue of its 2 electron-withdrawing chlorine groups, carbene (3) is highly


electron deficient and is attracted to the electron rich phenoxide (5). This interaction
favors selective ortho-formylation.
Reaction conditions
Hydroxides are generally not readily
soluble in chloroform, thus the
reaction is generally carried out in a
biphasic solvent system. In the
simplest sense this consists of an
aqueous hydroxide solution and an
organic phase containing the
chloroform. The two reagents are
therefore separated and must be
brought together for the reaction to
take place. This can be achieved by
rapid mixing, phase-transfer
catalysts, or an emulsifying agent (the
use of 1,4-dioxane as a solvent is an
example).
The mechanism of the Reimer-Tiemann reaction
The reaction typically needs to be
heated to initiate the process,
however once started the Reimer-
Tiemann Reaction can be highly exothermic, this combination makes it prone to
thermal runaways.

Scope
The Reimer–Tiemann reaction is effective for other hydroxy-aromatic compounds,
such as naphthols.[9] Electron rich heterocycles such as pyrroles and indoles are also
known to react.

Dichlorocarbenes can react with alkenes and amines to respectively form


dichlorocyclopropanes and isocyanides. As such the Reimer–Tiemann reaction may
be unsuitable for substrates bearing these functional groups. In addition, many
compounds can not withstand being heated in the presence of hydroxide.

Comparison to other methods


The direct formylation of aromatic compounds can be accomplished by various
methods such as the Gattermann reaction, Gattermann–Koch reaction, Vilsmeier–
Haack reaction, or Duff reaction; however, in terms of ease and safety of operations,
the Reimer–Tiemann reaction is often the most advantageous route chosen in
chemical synthesis. Of the reactions mentioned before, the Reimer–Tiemann reaction
is the only route not requiring acidic and/or anhydrous conditions.[3] Additionally the
Gattermann-Koch and Vilsmeier–Haack reactions are not applicable to phenol
substrates.

Variations
The Reimer–Tiemann reaction can be altered to yield phenolic acids by substituting
the chloroform with carbon tetrachloride.[10] For instance, the altered reaction with
phenol would yield salicylic acid rather than the expected product, salicylaldehyde.

References
1. Reimer, K.; Tiemann, Ferd. (1876). "Ueber die Einwirkung von Chloroform auf
Phenole und besonders aromatische Oxysäuren in alkalischer Lösung" (https://bab
el.hathitrust.org/cgi/pt?id=hvd.cl1hz1;view=1up;seq=240) [On the effect of
chloroform on phenols and particularly aromatic oxyacids in alkaline solution].
Berichte der Deutschen Chemischen Gesellschaft. 9 (2): 1268–1278.
doi:10.1002/cber.18760090270 (https://doi.org/10.1002%2Fcber.18760090270).
2. Wynberg, Hans (1960). "The Reimer-Tiemann Reaction". Chemical Reviews. 60 (2):
169–184. doi:10.1021/cr60204a003 (https://doi.org/10.1021%2Fcr60204a003).
3. Wynberg and Meijer, Egbert, Hans; Meijer, Egbert W. (2005). The Reimer–Tiemann
Reaction. p. 14. doi:10.1002/0471264180.or028.01 (https://doi.org/10.1002%2F04
71264180.or028.01). ISBN 9780471264187.
4. Dauben, William G. (1982). "The Reimer-Tiemann Reaction". Organic Reactions,
Volume 28. Hoboken, NJ: Wiley-Interscience. pp. 1–36.
doi:10.1002/0471264180.or028.01 (https://doi.org/10.1002%2F0471264180.or028.
01). ISBN 978-0471861416.
5. Wynberg, Hans (1991). The Reimer–Tiemann Reaction. Comprehensive Organic
Synthesis. 2. pp. 769–775. doi:10.1016/B978-0-08-052349-1.00048-2 (https://doi.o
rg/10.1016%2FB978-0-08-052349-1.00048-2). ISBN 978-0-08-052349-1.
6. Reimer, K. (1876). "Ueber eine neue Bildungsweise aromatischer Aldehyde" (http
s://babel.hathitrust.org/cgi/pt?id=hvd.cl1hyz;view=1up;seq=469) [On a new way
of forming aromatic aldehydes]. Berichte der Deutschen Chemischen Gesellschaft
(in German). 9: 423–424. doi:10.1002/cber.187600901134 (https://doi.org/10.100
2%2Fcber.187600901134).
7. Reimer, Karl (1883) "Sitzung vom 22. Januar 1883". Berichte der deutschen
chemischen Gesellschaft. 16, p. 101.
8. Hine, Jack; Van Der Veen, James M. (December 1959). "The Mechanism of the
Reimer-Tiemann Reaction". Journal of the American Chemical Society. 81 (24):
6446–6449. doi:10.1021/ja01533a028 (https://doi.org/10.1021%2Fja01533a028).
9. Russell, Alfred; Lockhart, Luther B. (1942). "2-HYDROXY-1-NAPHTHALDEHYDE".
Organic Syntheses. 22: 63. doi:10.15227/orgsyn.022.0063 (https://doi.org/10.1522
7%2Forgsyn.022.0063).
10. Gaonkar, A.V.; Kirtany, J.K. (2010). "ChemInform Abstract: Reimer-Tiemann
Reaction Using Carbon Tetrachloride". ChemInform. 22 (41): 1991.
doi:10.1002/chin.199141092 (https://doi.org/10.1002%2Fchin.199141092).

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