A Translator’s Guide to Organic Chemical

Nomenclature
Part XXVII

by Chester E. Claff, Jr., Ph. D.

 
 
Download the zipped version of installments 1 - 7 of this series, originally
published in the Sci-Tech Translation Journal of the American Translators
Association. The file is approximately 87 KB.

Installments 8 - 26 of this series appeared in the July 1997, October 1997,

January 1998, April 1998, July 1998, October 1998, January 1999, April 1999,
July 1999, October 1999, January 2000, April 2000, July 2000, October 2000,
January 2001, April 2001, July 2001, October 2001, and January 2002 issues
of the Translation Journal.
 

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 Part XXVI. Nonpolar organic solvents
such as benzene or aliphatic hydrocarbons are unable to coordinate with ions
and therefore cannot dissolve ionic substances.

In 1967, Charles J. Pederson at du Pont found that cyclic polyethers can

coordinate with metal ions such as K+ in nonpolar solvents, thus separating
them from their associated anions and rendering their salts soluble in these
solvents. When potassium permanganate (KMnO4), a useful oxidizing agent,
was subjected to the action of such a cyclic polyether, it became soluble in
benzene and was then available for use in an extended range of reactions.
Pederson assigned the trivial name "crown ethers" to this class of
coordinating agents, a nomenclature that has become standard.

Shown below are some typical crown ethers.

12-crown-4 (12-membered ring with 4 oxygen

atoms)

13-crown-4

15-crown-5

18-crown-6
 27-crown-9

dicyclohexyl-18-crown-6

The potassium permanganate complex of dicyclohexyl-18-crown-6 (a host-

guest complex) has the structure:

Pederson synthesized about 60 different crown ethers in the 1960s, and

found that the size of the central "cavity" determined which metal ions would
be complexed most strongly, depending on their size. Donald J. Cram at
UCLA then synthesized a large number of functionalized crown ethers of all
sizes and shapes and "delineated the principles of molecular architecture
needed for optimal binding and specificity" [Chem. Eng. News, January 2,
1984, p. 33].

Modified crown ethers with some of the oxygen atoms replaced by nitrogen
atoms are called cryptands.

The concept of size- 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 zeolites (aluminosilicates) as
selective adsorbents. These materials have cavities of diverse sizes and
shapes that selectively trap ions and molecules as a function of their specific
dimensions. They have found wide industrial use. Interested readers may
refer to Chem. Eng. News, December 13, 1982, pp. 9-15 for details on their
early uses and development.
 

Calixcrowns and calixarenes

The incorporation of benzene rings into crown ethers has led to the synthesis
of more complex ring systems such as bis(p-phenylene)-34-crown-10:

In turn, this has led to the development of calixarenes, cyclic complex-

forming polyphenols such as calix[6]arene, shown below:

Further information on these and other novel complexing agents, as well as

novel structures of potential use in nanotechnology, is available at
http://dochost.rz.hu-berlin.de/dissertationen/chemie/wendel-volker/,

a dissertation by Volker Wendel, with abstract in English and German and

full text in German, in HTML and PDF formats. Check out Chapters 4 and 7.
 

Miscellany

The structure of ciguatoxins, toxic compounds present in 400 species of fish,

has long been conjectured. However, definite proof has just been presented
by Prof. Masahiro Hirama of Tohoku University in Japan. In a project lasting
12 years, he and his graduate students synthesized a ciguatoxin, CTX3C,
from simple starting materials (Chemical & Engineering News, 79 No. 49,
12/3/01, p. 9). The compound has 13 rings with from five to nine members,
and 30 chiral centers. Surprisingly, none of the intermediates en route to the
compound were toxic. Toxicity was found only after the final step of
removing protective groups. The synthesis is all the more remarkable since
about a billion stereoisomers could exist, and the group produced the only
one found in fish.