9/14/2016 Crown ether - Wikipedia, the free encyclopedia

Crown ether
From Wikipedia, the free encyclopedia

Crown ethers are cyclic chemical compounds that consist of a ring containing several ether
groups. The most common crown ethers are oligomers of ethylene oxide, the repeating unit
being ethyleneoxy, i.e., –CH2CH2O–. Important members of this series are the tetramer
(n = 4), the pentamer (n = 5), and the hexamer (n = 6). The term "crown" refers to the
resemblance between the structure of a crown ether bound to a cation, and a crown sitting
on a person's head. The first number in a crown ether's name refers to the number of atoms
in the cycle, and the second number refers to the number of those atoms that are oxygen.
Crown ethers are much broader than the oligomers of ethylene oxide; an important group are
derived from catechol.

Crown ethers strongly bind certain cations, forming complexes. The oxygen atoms are well
situated to coordinate with a cation located at the interior of the ring, whereas the exterior of 18-crown-6 coordinating a
the ring is hydrophobic. The resulting cations often form salts that are soluble in nonpolar potassium ion
solvents, and for this reason crown ethers are useful in phase transfer catalysis. The denticity
of the polyether influences the affinity of the crown ether for various cations. For example,
18-crown-6 has high affinity for potassium cation, 15-crown-5 for sodium cation, and 12-crown-4 for lithium cation. The high
affinity of 18-crown-6 for potassium ions contributes to its toxicity. Crown ethers are not the only macrocyclic ligands that have
affinity for the potassium cation. Ionophores such as valinomycin also display a marked preference for the potassium cation over
other cations.

Structures of common crown ethers: 12-crown-4, 15-crown-5, 18-crown-6, dibenzo-18-crown-6, and diaza-18-crown-6.

Contents

1 History

2 Affinity for cations

3 Azacrowns

4 See also

5 References

6 External links

History

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In 1967, Charles Pedersen, who was a chemist working at DuPont, discovered a simple method of synthesizing a crown ether
when he was trying to prepare a complexing agent for divalent cations.[1][2] His strategy entailed linking two catecholate groups
through one hydroxyl on each molecule. This linking defines a polydentate ligand that could partially envelop the cation and, by
ionization of the phenolic hydroxyls, neutralize the bound dication. He was surprised to isolate a by-product that strongly complexed
potassium cations. Citing earlier work on the dissolution of potassium in 16-crown-4,[3][4] he realized that the cyclic polyethers
represented a new class of complexing agents that were capable of binding alkali metal cations. He proceeded to report systematic
studies of the synthesis and binding properties of crown ethers in a seminal series of papers. The fields of organic synthesis, phase
transfer catalysts, and other emerging disciplines benefited from the discovery of crown ethers. Pedersen particularly popularized
the dibenzo crown ethers.[5]

Pedersen shared the 1987 Nobel Prize in Chemistry for the discovery of the synthetic routes to, and binding properties of, crown
ethers.

Affinity for cations

Apart from its high affinity for potassium cations, 18-crown-6 can also bind to protonated amines and form very stable complexes
in both solution and the gas phase. Some amino acids, such as lysine, contain a primary amine on their side chains. Those
protonated amino groups can bind to the cavity of 18-crown-6 and form stable complexes in the gas phase. Hydrogen-bonds are
formed between the three hydrogen atoms of protonated amines and three oxygen atoms of 18-crown-6. These hydrogen-bonds
make the complex a stable adduct. By incorporating luminescent substituents into their backbone, these compounds have proved to
be sensitive ion probes, as changes in the absorption or fluorescence of the photoactive groups can be measured for very low
concentrations of metal present.[6] Some attractive examples include macrocycles, incorporating oxygen and/or nitrogen donors,
that are attached to polyaromatic species such as anthracenes (via the 9 and/or 10 positions)[7] or naphthalenes (via the 2 and 3
positions).[8]

Azacrowns
21- and 18-membered diazacrown ether derivatives exhibit excellent calcium and magnesium selectivities and are widely used in
ion-selective electrodes.[9] Some or all of the oxygen atoms in crown ethers can be replaced by nitrogens to form cryptands. A
well-known tetrazacrown is cyclen in which there are no oxygens.[10]

Lariat crown ethers have sidearms that can augment complexation of cation. The lariat is typically attached to an amine centre in an
azacrown.[11]

See also
Cryptand
Metallacrown

References
1. Pedersen, C. J. (1967). "Cyclic polyethers and their complexes with metal salts". Journal of the American Chemical Society. 89
(26): 7017–7036. doi:10.1021/ja01002a035.
2. Pedersen, C. J. (1967). "Cyclic polyethers and their complexes with metal salts". Journal of the American Chemical Society. 89
(10): 2495–2496. doi:10.1021/ja00986a052.
3. GB 785229 (http://worldwide.espacenet.com/textdoc?DB=EPODOC&IDX=GB785229), Stewart, D. G.; D. Y. Waddan & E. T.
Borrows,
4. Down, J. L.; Lewis, J.; Moore, B.; Wilkinson, G. (1959). "761. The solubility of alkali metals in ethers". Journal of the Chemical
Society: 3767. doi:10.1039/jr9590003767.
5. Pedersen, Charles J. (1988). "Macrocyclic Polyethers: Dibenzo-18-Crown-6 Polyether and Dicyclohexyl-18-Crown-6 Polyether".
Org. Synth.; Coll. Vol., 6, p. 395

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9/14/2016 Crown ether - Wikipedia, the free encyclopedia
6. Fabbrizzi, L.; Francese, G.; Licchelli, M.; Pallavicini, P.; Perotti, A.; Poggi, A.; Sacchi, D.; Taglietti, A. (1997). Desvergne, J. P.;
Czarnik, A. W., eds. Chemosensors of Ion and Molecule Recognition. NATO ASI Series C. 492. Dordrecht: Kluwer Academic
Publishers. p. 75.
7. Bouas-Laurent, H.; Desvergne, J. P.; Fages, F.; Marsau, P. (1993). A. W., Czarnik, ed. Fluorescent Chemosensors for Ion and
Molecule Recognition. ACS Symposium Series 538. Washington, DC: American Chemical Society. p. 59.
8. Sharghi, Hashem; Ebrahimpourmoghaddam, Sakineh (2008). "A Convenient and Efficient Method for the Preparation of Unique
Fluorophores of Lariat Naphtho-Aza-Crown Ethers". Helvetica Chimica Acta. 91 (7): 1363–1373. doi:10.1002/hlca.200890148.
9. Suzuki, K.; Watanabe, K.; Matsumoto, Y.; Kobayashi, M.; Sato, S.; Siswanta, D.; Hisamoto, H. (1995). "Design and Synthesis of
Calcium and Magnesium Ionophores Based on Double-Armed Diazacrown Ether Compounds and Their Application to an Ion
Sensing Component for an Ion-Selective Electrode". Anal. Chem. 67 (2): 324–334. doi:10.1021/ac00098a016.
10. Gatto, Vincent J.; Miller, Steven R.; Gokel, George W. (1988). "4,13-Diaza-18-Crown-6". Org. Synth.; Coll. Vol., 8, p. 152
11. Gokel, G. W.; Barbour, L. J.; Ferdani, R.; Hu, J. (2002). "Lariat Ether Receptor Systems Show Experimental Evidence for Alkali
Metal Cation Interactions". Acc. Chem. Res. 35: 878–886. doi:10.1021/ar000093p.

External links
Pedersen, Charles (1987). "Nobel Lecture" (PDF). Nobel Prize.
Molecular crown (http://www.org-chem.org/yuuki/crown/crown_en.html)

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Categories: Crown ethers

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