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Oxygen crown ether compounds

It was shown that 2,5-bis(phenoxy)-3,3aA4,4-trithia-l,6-diazapentalene 182 reacts with , v-diami nopolyether nucleophiles 183 in a 1 1 molar ratio to form novel pentaleno crown ethers 184 (see Scheme 21 and Table 24) <1997AG(E)1648>. Macrocycles 184 were readily reduced by treatment with zinc in acetic acid to form the corresponding thioureas 185. The reoxidation is quantitative in the presence of atmospheric oxygen. The complex formation of the starting pentalene 182 and the new crown ether compounds 184 and 185 was investigated (see Section 12.11.7.2). [Pg.517]

The highest coordination state of Mg is hexacoordinate, even when further intramolecular coordination is possible. The Mg of the crown ether compound, 2-bromomagnesio-l,3-xylyl-18-crown-5 [Compound 16] [17], is coordinated to only four of the five oxygen atoms as well as the Br and the aromatic carbon. [Pg.124]

Comparison of the data for the lipophilic diazacrown ethers in Table 2 with that for the analogous crown ether compounds in Table 1 shows that replacement of two oxygen atoms in the macrocyclic ring with NH or NC2H5 units drastically reduces the alkali metal perchlorate transport. Presumably this results from diminished complexation of the hard alkali metal cations by the macrocyclic ligands when two hard oxygen donor sites are replaced by two nitrogen atoms. [Pg.161]

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... [Pg.669]

The metal-ion complexmg properties of crown ethers are clearly evident m their effects on the solubility and reactivity of ionic compounds m nonpolar media Potassium fluoride (KF) is ionic and practically insoluble m benzene alone but dissolves m it when 18 crown 6 is present This happens because of the electron distribution of 18 crown 6 as shown m Figure 16 2a The electrostatic potential surface consists of essentially two regions an electron rich interior associated with the oxygens and a hydrocarbon like exterior associated with the CH2 groups When KF is added to a solution of 18 crown 6 m benzene potassium ion (K ) interacts with the oxygens of the crown ether to form a Lewis acid Lewis base complex As can be seen m the space filling model of this... [Pg.669]

The unique chemical behavior of KO2 is a result of its dual character as a radical anion and a strong oxidizing agent (68). The reactivity and solubiHty of KO2 is gready enhanced by a crown ether (69). Its usefiilness in furnishing oxygen anions is demonstrated by its appHcations in SN2-type reactions to displace methanesulfonate and bromine groups (70,71), the oxidation of benzyHc methylene compounds to ketones (72), and the syntheses of a-hydroxyketones from ketones (73). [Pg.519]

Another group of macrocyclic ligands that have been extensively studied are the cycHc polyethers, such as dibenzo-[18]-crown-6 (5), in which the donor atoms are ether oxygen functions separated by two or three carbon atoms. The name crown ethers has been proposed (2) for this class of compounds because of the resemblance of their molecular models to a crown. Sandwich stmctures are also known in which the metal atom is coordinated with the oxygen atoms of two crown molecules. [Pg.382]

Related to the crown ethers are compounds, such as hexamethyl-[14]-4,ll-diene (6), which differ by the replacement of one or more of the oxygen atoms by other kinds of donor atoms, particularly N or S. MacrocycHc amine and thioether compounds have been synthesized. Compounds having more than one kind of heteroatom in the ring are called mixed-donor macrocycles. The naturally occurring metaboUtes nonactin [6833-84-7] and monactin [7182-54-9] have both ether and ester groups incorporated in the macrocyclic stmcture. [Pg.382]

Dipotassium phthalocyanine (PcK2) can be prepared analogously to the dilithium compound by refluxing phthalonitrile and potassium pentoxide in pentan-l-ol.58 With additional oxygen-donor ligands (e.g., crown ethers) it forms crystals with the potassium bulging outside of the phthalocyanine ring.133134... [Pg.728]

In [Tl 18-crown-6] [CIO4] (Fig. 2.1), the thallium(I) cation resides 75 pm above the plane defined by the oxygen atoms of the crown ether and 66 pm in [ri 18-crown-6] [TII4] [39] whereas, for example, in the analogous potassium compound [K 18-crown-6] [CIO4] [40] the cation is found right in the middle of the crown ether (Fig. 2.2). [Pg.19]

Crown-ethers can incorporate protonated primary amine compounds by formation of ion-dipole bonds with the oxygen atoms of the chiral selector. Crown-ethers have been widely used for the separation of several pharmaceuticals both in aqueous and non-aqueous media." ... [Pg.460]


See other pages where Oxygen crown ether compounds is mentioned: [Pg.370]    [Pg.186]    [Pg.1178]    [Pg.3]    [Pg.3017]    [Pg.86]    [Pg.221]    [Pg.348]    [Pg.670]    [Pg.167]    [Pg.2]    [Pg.267]    [Pg.417]    [Pg.670]    [Pg.339]    [Pg.169]    [Pg.144]    [Pg.155]    [Pg.105]    [Pg.78]    [Pg.115]    [Pg.225]    [Pg.913]    [Pg.1161]    [Pg.66]    [Pg.15]    [Pg.320]    [Pg.316]    [Pg.319]    [Pg.6]    [Pg.280]    [Pg.280]    [Pg.368]    [Pg.382]    [Pg.423]    [Pg.14]    [Pg.94]    [Pg.6]   
See also in sourсe #XX -- [ Pg.95 , Pg.96 , Pg.124 , Pg.601 ]

See also in sourсe #XX -- [ Pg.95 , Pg.96 , Pg.124 , Pg.601 ]




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Compounds oxygenated

Crown compounds

Ethers compounds

Oxygen compounds

Oxygenate compounds

Oxygenous compound

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