Allyl-substituted macrocyclic crown formazans: Promising precursors for polymer-supported macrocycles

The bisphenol 1 was obtained by reacting the amine hydrochloride 11 with cy anoacetic acid in aqueous sodium hydroxide solution. Thermal rearrangement of 1,5-bis(allyloxyphenyl)formazan (7) failed to give 1. Alkylation of the bis phenol 1 with 1,3-dibromopropane in basic solution under high dilution conditions gave the corresponding allyl-substituted macrocyclic formazan 2a in a very low yield. On the other hand, diazotization of the new bis amine hydrochloride 3a,b with NaNO2 in hydrochloric acid followed by coupling wi th the appropriate active methylene compounds furnished the corresponding m acrocyclic formazans 2a-d. Compounds 3a,b were obtained by first reacting t he K-salt of 12 with the appropriate dihalides to give the corresponding bi s acetamides 13 and 14, respectively. Subsequent acid hydrolysis of the lat ter afforded 3a,b in good yield.