Allyl-Substituted Macrocyclic Crown Formazans: Promising Precursors for Polymer-Supported Macrocycles

Abstract

The bisphenol 1 was obtained by reacting the amine hydrochloride 11 with cyanoacetic 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 with the appropriate active methylene compounds furnished the corresponding macrocyclic formazans 2a-d. Compounds 3a ,b were obtained by first reacting the K-salt of 12 with the appropriate dihalides to give the corresponding bis acetamides 13 and 14, respectively. Subsequent acid hydrolysis of the latter afforded 3a,b in good yield.

Key words

alkylation - thermal rearrangement - diazotization - coupling - macrocyclic formazans

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