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Synthesis of Diazacrown Ethers Containing Phenolic Side Arms and Their Complex with Divalent Metal Ions

  • Published : 2002.05.20
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Abstract

The aminomethylation of phenols with para-substituents by the Mannich reaction has successfully been accomplished to produce the Mannich bases 2-6. The compounds 7-8 have also been synthesized in order to identify the effect of the side arms and t he macrocycle in the complex formation. Protonation constants and stability constants of the double armed diaza-18-crown-6 ethers 2-7 with metal ions have been determined by potentiometric method at 25 $^{\circ}C$ in 95 % methanol solution. Under a basic condition (pH > 8.0), the double-armed crown ethers 2-6 revealed stronger interaction with divalent metal ions than the simple diazacrown ether 1. The stability constants with these metal ions were Co 2+ < Ni2+ < Cu2+ > Zn 2+ in increasing order, which are in accordance with the order of the Williams-Irving series. The stability constants with alkali earth metal ions were Ca 2+ < Sr 2+ < Ba 2+ in increasing order, which may be explained by the concept of size effect. It is noteworthy that the hosts 2-6, which have phenolic side arms and a macrocycle, bind stronger with metal ions than the hosts 1 and 7. On the other hand, the host 8, which has phenolic side arms with a pyperazine ring,provided comparable stability constants to those with the host 3. These facts demonstrate that phenolic side arms play a more important role than the azacrown ether ring in the process of making a complex with metal ions especially in a basic condition. In particular, the log KML values for complexation of divalent metal ions with the hosts 2-6 had the sequence, i.e., 2 (R=OCH3) < 3 (R=CH3) < 4 (R=H) < 5 (R=Cl) < 6 (R=CF3). The stability constants of the hosts 5 and 6 containing an electron-withdrawing group are larger than those of the hosts 2 and 3 containing an electron-donating group. This substituent effect is attributed to the solvent effect in which the aryl oxide with an electron-donating group has a tendency to be tied strongly with protic solvents.

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