Crown ethers Many reagents useful for organic synthesis are soluble in water because of their ionic nature,

but are insoluble in organic solvents for the same reason. However, most organic syntheses are performed in organic solvents, and it would therefore give chemists more flexibility to be able to use ionic reagents in these media. Solubility in water is generally driven by hydration of cations to separate them from their associated anions, as pointed out in previous installments of this series. Hydration in turn is driven by the formation of non-covalent bonds (complexing, coordination ! see "art ##$%. &onpolar organic solvents such as ben'ene or aliphatic hydrocarbons are unable to coordinate with ions and therefore cannot dissolve ionic substances. %n ()*+, Charles ,. "ederson at du "ont found that cyclic polyethers can coordinate with metal ions such as -. in nonpolar solvents, thus separating them from their associated anions and rendering their salts soluble in these solvents. /hen potassium permanganate (-Mn01 , a useful oxidi'ing agent, was sub2ected to the action of such a cyclic polyether, it became soluble in ben'ene and was then available for use in an extended range of reactions. "ederson assigned the trivial name 3crown ethers3 to this class of coordinating agents, a nomenclature that has become standard. Shown below are some typical crown ethers.

(4-crown-1 ((4-membered ring with 1 oxygen atoms

(5-crown-1

(6-crown-6

(7-crown-*

4+-crown-)

dicyclohexyl-(7-crown-* 8he potassium permanganate complex of dicyclohexyl-(7-crown-* (a host-guest complex has the structure9

"ederson synthesi'ed about *: different crown ethers in the ()*:s, and found that the si'e of the central 3cavity3 determined which metal ions would be complexed most strongly, depending on their si'e. ;onald ,. Cram at <C=> then synthesi'ed a large number of functionali'ed crown ethers of all si'es and shapes and 3delineated the principles of molecular architecture needed for optimal binding and specificity3 ?Chem. @ng. &ews, ,anuary 4, ()71, p. 55A. Modified crown ethers with some of the oxygen atoms replaced by nitrogen atoms are called cryptands.

8he concept of si'e- and shape-selective trapping, complexing, and catalysis, analogous in some respects to the use of crown ethers, has been extended to using natural and synthetic inorganic 'eolites (aluminosilicates as selective adsorbents. 8hese materials have cavities of diverse si'es and shapes that selectively trap ions and molecules as a function of their specific dimensions. 8hey have found wide industrial use. %nterested readers may refer to Chem. @ng. &ews, ;ecember (5, ()74, pp. )-(6 for details on their early uses and development. Calixcrowns and calixarenes 8he incorporation of ben'ene rings into crown ethers has led to the synthesis of more complex ring systems such as bis(p-phenylene -51-crown-(:9

%n turn, this has led to the development of calixarenes, cyclic complex-forming polyphenols such as calix?*Aarene, shown below9

/hat is a Crown @therB

Model of Crown @ther > crown ether is a molecule containing hydrogen, carbon and oxygen atoms. @ach oxygen atom is bound between two of the carbon atoms and arranged in a ring (hence 3crown3 . 8he original crown ether discovered by Charles "edersen has six oxygen atoms exposed along the inside wall of the ring. /hen atoms of certain metalic elements such as sodium or potassium pass through the center of the ring, they attach themselves to the exposed oxygen atoms and fit liCe a Cey in a locC. 8he crown compound then acts as 3host,3 taCing its 3guest3 to a place where it would not otherwise go - for instance, through the membrane that forms the wall of a cell. 8he high degree of selectivity enables the crown compound to 3identify3 the guest atom in a solution and wrap around it. %n accepting specific atoms locC and Cey fashion, crown ethers mimic in a relatively uncomplicated way the very complicated functions of biological materials such as en'ymes. %t is this mimicry that has scientists so excited. 8he study of crown compounds may indicate new approaches for developing pharmaceutical systems or a way to cross the blood-brain barrier. 8hey may help explain how the body moves sodium and potassium, essential elements for life, into cells. Crown ethers also have potential to be used as 3scavengers3 to remove certain elements liCe radioactive strontium from the environment or to regulate concentrations of sodium in the blood. Some people have even suggested that crown compounds could be used one day to extract uranium or gold from seawater