Synthesis of novel lariat azathia crown macrocycles containing two triazole rings and bis crown macrocycles containing four triazole rings

The 13-hydroxy macrocycles 7a-d were prepared in 40-50% yields by the condensation of 1,omega-bis(4-amino-1,2,4-triazol-3-ylsulfany)alkanes 2a-d with 1,3-bis(2-formyphenoxy)-2-propanol (9). Acylation of 7a-d with 2-chloroacetylchloride gave the corresponding esters 11a,b. Amination of 11a,b with different amines in acetone furnished exclusively the target lariat macrocycles 12a,b and 13 in 60-70% yields. Reaction of 2 equiv. of the macrocycles 11a,b with I equiv. of piperazine afforded the novel his macrocyles 14a,b in 50-60% yields. Reduction of 7a-d with NaBH4 afforded the corresponding 13-hydroxyazathia crown ethers 15a-d in 65-70% yields. (C) 2003 Elsevier Ltd. All rights reserved.