The literature procedures for the targeted syntheses of p-tert-butylcalixarene, p-tert-butylcalixarene, p-tert-butylcalixarene, p-tert-butylcalixarene, and p-tert-butylcalixarene have been repeated successfully. In the case of p-tert-butylcalixarene, alterations led to a less capricious procedure, synthesis of the pure product directly and in higher yield. The residual xylene and toluene solutions from the targeted p-tert-butylcalixarene preparation were utilised to obtain workable quantities of the rare calix- and calixarenes, a protocol that is far simpler and less time-consuming than the low-yielding targeted synthesis of these compounds. Dealkylation of p-tert-butylcalix[n]arenes is best accomplished at 30°C in 0.16-0.05 molL−¹ toluene solution. The insolubility of calixarene in all common organic solvents is expected to limit its synthetic use. Two new protocols have been devised for the highly selective mono-O-alkylation of calixarenes 4 through 8. This work represents the realisation of the first selective functionalisation methods that are applicable to the calixarene family, and also the first selective functionalisation of a calixarene. These findings will lead to more efficient synthesis of multiple calixarenes (cf. Chapter 3) and may allow for a better understanding of the reasons for selectivity in calixarene-O-alkylations. We have been able to synthesise a variety of bis-calixarenes by two different routes. Glaser-Hay coupling allowed the synthesis of symmetrical diyne bridged bis-calix[4, 6 and 8]arenes in high yield. Extension of the first general mono-O-alkylation procedure for calixarenes has made it possible to synthesise hom o-bis-calixarenes in good yield in one step from the parent calixarenes. The unexpected formation of monobromoxylyl calixarenes allows the prospect of the synthesis of hetero-bis-calixarenes under more forcing conditions. Most importantly this allows us to further explore the chemistry of bis-calixarenes by making them readily available (in large quantities) for more elaborate syntheses.