Calix[4, 5]tetrolarenes: A New Family of Macrocycles

The
facile and efficient one-step synthesis and the full characterization
of novel π-electron rich macrocycles, calix-[n]­tetrolarenes (n = 4, 5), are described. The tetramer
and the much rarer sized pentamer were easily prepared by reaction
of the commercially available, partially methylated 1,2,3,5-benzenetetrol
with paraformaldehyde under TFA catalysis, with a total isolated yield
of 73%. The reaction is solvent sensitive, and the number of methylated
oxygens also affects the tetramer/pentamer distribution. The compounds
formed may be considered as “chimeric” macrocycles of
calixarene and pyrogallol­[n]­arene that may serve
as new building blocks in host–guest and supramolecular chemistry.

本文报道了一类新型富π电子大环化合物——杯[n]四酚芳烃（calix-[n]tetrolarenes，n=4、5）的简便高效一步合成法与完整表征结果。该四聚体与较为罕见的五聚体可通过商业可得的部分甲基化1,2,3,5-苯四酚与多聚甲醛在三氟乙酸（TFA）催化下的反应便捷制备，总分离产率可达73%。该反应对溶剂具有敏感性，且甲基化氧原子的数目同样会影响四聚体与五聚体的产物分布比例。所合成的这类化合物可被视为杯芳烃（calixarene）与焦棓酚[n]芳烃的嵌合型大环，有望作为主客体化学与超分子化学领域的新型构筑基元。