Aa. Abbas et Ahm. Elwahy, Allyl-substituted macrocyclic crown formazans: Promising precursors for polymer-supported macrocycles, SYNTHESIS-S, (9), 2001, pp. 1331-1336
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.