Syntheses, crystal structures, and metal ion complexation studies of novel diaza-18-crown-6 ligands containing aromatic thiol-derived side arms

✍ Scribed by Ning Su; Jerald S. Bradshaw; Guoping Xue; N. Kent Dalley; Xian X. Zhang; Paul B. Savage; Krzysztof E. Krakowiak; Reed M. Izatt

• Publisher: Journal of Heterocyclic Chemistry
• Year: 2000
• Tongue: English
• Weight: 516 KB
• Volume: 37
• Category: Article
• ISSN: 0022-152X
• DOI: 10.1002/jhet.5570370407

✦ Synopsis

Abstract

The Mannich aminomethylation reaction of aromatic thiols has been used to produce diaza‐18‐crown‐6 ligands containing thiol‐derived side arms. Thiophenols were attached to the azacrown through N‐CH~2~‐S linkages even in the presence of hydroxy or acetamido groups. Heteroaromatic thiols containing N=C‐SH (or NH‐C=S) structural fragments were attached to diaza‐18‐crown‐6 by N‐CH~2~‐N linkages with the thiol becoming a thione function. X‐ray crystal structural analyses show the N‐CH~2~‐S and N‐CH~2~‐N linkages for some of the new macrocyclic compounds. Interactions of four of the new diaza‐18‐crown‐6 ligands with Na^+^, K^+^, Ba^2+^, Ag^+^, Zn^2+^, Cd^2+^, Ni^2+^, and Cu^2+^ were evaluated by calorimetric titration at 25° in methanol. The results show that these ligands form stable complexes with many of the metal ions studied.