New diazadi(and tri)thia-21-crown-7 ethers containing 8-hydroxyquinoline side arms

✍ Scribed by Hua-Can Song; Yi-Wen Chen; Ji-Guo Song; Paul B. Savage; Guo-Ping Xue; Joseph A. Chiara; Reed M. Izatt; Jerald S. Bradshaw; Krzysztof E. Krakowiak

• Book ID: 102337945
• Publisher: Journal of Heterocyclic Chemistry
• Year: 2001
• Tongue: English
• Weight: 102 KB
• Volume: 38
• Category: Article
• ISSN: 0022-152X
• DOI: 10.1002/jhet.5570380619

✦ Synopsis

Abstract

A series of macrocyclic diazadi(and tri)thiacrown ethers containing two 5‐substituent‐8‐hydroxyquinoline side arms have been synthesized from the corresponding macrocyclic diazadi(and tri)thiacrown ethers. The crown ethers were obtained by reduction of the proper macrocyclic di(and tri)thiadiamides by borane‐tetrahydrofuran or by sodium borohydride‐boron trifluoride ethyl etherate‐tetrahydrofuran. The yields for the reduction of diamides by sodium borohydride‐boron trifluoride ethyl etherate‐tetrahydrofuran were higher than those by borane‐tetrahydrofuran. The following four methods were used to prepare macrocycles bearing two 8‐hydroxyquinoline side arms: (1) Mannich reaction with 8‐hydroxyquinoline; (2) Reductive animation with 8‐hydroxyquinoline‐2‐carboxaldehyde using sodium triacetoxyborohydride as the reducing agent; (3) Cyclization of N,N'‐bis(8‐hydroxyquinolin‐2‐ylmethyl)‐1,2‐bis(2‐aminoethoxy)ethane (38) with bis(α‐chloroamide) 5; and (4) A step‐by‐step process wherein macrocyclic trithiadiamide 11 was reduced by lithium aluminum hydride‐tetrahydrofuran to the cyclic monoamide 36, which smoothly reacted with 5‐chloro‐8‐hydroxyquinoline to produce monosubstituted‐macrocyclic monoamide 39.