Polyethers cyclic

The strength of this bonding depends on the kind of ether Simple ethers form relatively weak complexes with metal ions but Charles J Pedersen of Du Pont discovered that cer tain polyethers form much more stable complexes with metal ions than do simple ethers Pedersen prepared a series of macrocyclic polyethers cyclic compounds contain mg four or more oxygens m a ring of 12 or more atoms He called these compounds crown ethers, because their molecular models resemble crowns Systematic nomencla ture of crown ethers is somewhat cumbersome and so Pedersen devised a shorthand description whereby the word crown is preceded by the total number of atoms m the ring and is followed by the number of oxygen atoms... 

In another series of papers, published by Yamashita a.o. and describing macrocyclization in the cationic polymerization of oxiranes, much more complicated mixture of cyclic products was observed. Besides typical macrocyclic polyethers ° cyclic oligomers having acetal structure were found. These products can be fom d, according to Yam hita, as a result of back-biting to the rearranged growing species ... 

Reaction of alkylalumlnlum halides with polyethers. cyclic polyamlnes and quaternary ammonium salts, H.S. Elgamal, Piss. Abatr. Int B. 1986, Ifi., 2299 Chem. Abstr.. 1986, 105. 153112z. 

Crown 4 and 18 crown 6 are a cyclic tetramer and hexamer respectively of repeat mg —OCH2CH2— units they are polyethers based on ethylene glycol (HOCH2CH2OH) as the parent alcohol... 

Since 1950 a number of polyether antibiotics have been discovered using fermentation technol ogy They are characterized by the presence of sev eral cyclic ether structural units as illustrated for the case of monensm in Figure 16 3a Monensin and other naturally occurring polyethers are similar to crown ethers in their ability to form stable complexes... 

Ethers form Lewis acid Lewis base complexes with metal ions Certain cyclic polyethers called crown ethers, are particularly effective m coor dinatmg with Na" and K" and salts of these cations can be dissolved m nonpolar solvents when crown ethers are present Under these conditions the rates of many reactions that involve anions are accelerated... 

Critical micelle concentration (Section 19 5) Concentration above which substances such as salts of fatty acids aggre gate to form micelles in aqueous solution Crown ether (Section 16 4) A cyclic polyether that via lon-dipole attractive forces forms stable complexes with metal 10ns Such complexes along with their accompany mg anion are soluble in nonpolar solvents C terminus (Section 27 7) The amino acid at the end of a pep tide or protein chain that has its carboxyl group intact—that IS in which the carboxyl group is not part of a peptide bond Cumulated diene (Section 10 5) Diene of the type C=C=C in which a single carbon atom participates in double bonds with two others... 

Cyclic ether and acetal polymerizations are also important commercially. Polymerization of tetrahydrofuran is used to produce polyether diol, and polyoxymethylene, an excellent engineering plastic, is obtained by the ring-opening polymerization of trioxane with a small amount of cycHc ether or acetal comonomer to prevent depolymerization (see Acetal resins Polyethers, tetrahydrofuran). 

Polyether Polyols. Polyether polyols are addition products derived from cyclic ethers (Table 4). The alkylene oxide polymerisation is usually initiated by alkah hydroxides, especially potassium hydroxide. In the base-catalysed polymerisation of propylene oxide, some rearrangement occurs to give aHyl alcohol. Further reaction of aHyl alcohol with propylene oxide produces a monofunctional alcohol. Therefore, polyether polyols derived from propylene oxide are not truly diftmctional. By using sine hexacyano cobaltate as catalyst, a more diftmctional polyol is obtained (20). Olin has introduced the diftmctional polyether polyols under the trade name POLY-L. Trichlorobutylene oxide-derived polyether polyols are useful as reactive fire retardants. Poly(tetramethylene glycol) (PTMG) is produced in the acid-catalysed homopolymerisation of tetrahydrofuran. Copolymers derived from tetrahydrofuran and ethylene oxide are also produced. 

Some of these compounds could be considered as dietary additives, but various other terms, including pesticides, can also be used. They can have beneficial effects on the environment and this aspect will be discussed later. The ionophore monensin, which is an alicyclic polyether (Figure 1), is a secondary metabolite of Streptomyces and aids the prevention of coccidiosis in poultry. Monensin is used as a growth promoter in cattle and also to decrease methane production, but it is toxic to equine animals. " Its ability to act as an ionophore is dependent on its cyclic chelating effect on metal ions. ° The hormones bovine somatotropin (BST) and porcine somatotropin (PST), both of which are polypeptides, occur naturally in lactating cattle and pigs, respectively, but can also be produced synthetically using recombinant DNA methods and administered to such animals in order to increase milk yields and lean meat production. "... 

From their structures, it appears that the hydrolytic stability of macrocyclic lactones must necessarily be inferior to macrocyclic polyethers. Ease of synthesis of the cyclic esters is therefore one of the aspects which commend them to interest. It is probably for this reason that such lactones have not been made more often by the interesting approach of Kdgel and Schroder . These workers report the ozonolysis of dibenzo-18-crown-6 in a mixture of methanol and dichloromethane at —20°. Reduction of the ozon-ide at —75° using dimethylsulfide followed by warming and addition of acetone led to formation of 6 in 14% yield. The bis-oxalate had mp 164—165° from acetone, very similar to that of the starting crown. The transformation is illustrated below in Eq. (5.9). 

In specific applications to phase transfer catalysis, Knbchel and his coworkers compared crown ethers, aminopolyethers, cryptands, octopus molecules ( krakenmole-kiile , see below) and open-chained polyether compounds. They determined yields per unit time for reactions such as that between potassium acetate and benzyl chloride in acetonitrile solution. As expected, the open-chained polyethers were inferior to their cyclic counterparts, although a surprising finding was that certain aminopolyethers were superior to the corresponding crowns. 

Cram has published several studies indicating that complexation of ammonium salts was greatly enhanced by using cyclic polyethers over the corresponding acyclic ones. These molecules were analogs of the binaphthyl systems under study and were generally prepared by phenoxide substitution on the appropriate tosylate. The approach is illustrated below in Eq. (7.9). ... 

Crown ether (Section 16.4) A cyclic polyether that, via ion-dipole attractive forces, forms stable complexes with metal ions. Such complexes, along with their accompanying anion, are soluble in nonpolar solvents. 

Crown ethers are cyclic polyethers. Larger crown ethers contain a cavity that can partially engulf atomic ions. 18-crown-6 actually binds so tightly that it can extract this ion into benzene from water, driving counterions, like MnOc, into the benzene layer, i.e. 

Cholanic acid also possesses the ability of transporting cations across a lipophilic membrane but the selectivity is not observed because it contains no recognition sites for specific cations. In the basic region, monensin forms a lipophilic complex with Na+, which is the counter ion of the carboxylate, by taking a pseudo-cyclic structure based on the effective coordination of the polyether moiety. The lipophilic complex taken up in the liquid membrane is transferred to the active region by diffusion. In the acidic region, the sodium cation is released by the neutralization reaction. The cycle is completed by the reverse transport of the free carboxylic ionophore. 

In mimicking this type of function, noncyclic artificial carboxylic ionophores having two terminal groups of hydroxyl and carboxylic acid moieties were synthesized and the selective transport of alkali metal cations were examined by Yamazaki et al. 9 10). Noncyclic polyethers take on a pseudo-cyclic structure when coordinating cations and so it is possible to achieve the desired selectivity for specific cations by adjusting the length of the polyether chain 2). However, they were not able to observe any relationship between the selectivity and the structure of the host molecules in an active transport system using ionophores 1-3 10). (Table 1)... 

Aldehydes Propionates Cyclic polyethers a-Amino acids Hydroperoxides C2H5, CHO... 

Aliphatic carboxylic acids Alkyl ethyl ethers Cyclic polyethers Phosphorous compounds Rearrangement peak in dioxanes... 

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