An examination of the synthesis and complexation properties of selected macrocyclic compounds

Giddings, Sabrina Dawn (2003) An examination of the synthesis and complexation properties of selected macrocyclic compounds. Masters thesis, Memorial University of Newfoundland.

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Abstract

Calix[4]naphthalenes are "basket shaped" molecules capable of supramolecular complexation with neutral species such as C₆₀. They were first synthesized by Li and Georghiou in 1993. Over the past decade much progress has been made towards developing practical synthetic routes to other regioisomeric calixnaphthalenes. To date, the best synthetic route involves a "one-pot" TiCl₄-mediated cyclocondensation of 3-(hydroxymethyl)-2-naphthol, but affords low yields. Since the chemical properties of calix[4]naphthalenes need to be fully explored, there is a need for more efficient methods of synthesizing these types of compounds. -- Ionic liquids, have shown great potential for use in organic synthesis. Several reports have been published which describe the efficient synthesis of cyclotriveratrylene, another basket shaped compound of interest, in ionic liquids. ²⁹,³⁰ In principle, the methodology employed could be applicable to the synthesis of calix[4]naphthalenes. We therefore explored the use of ionic liquids for their synthesis of calix[ 4]naphthalenes. -- Recently, an unusual method for synthesizing the related calix[4]azulene was reported. This synthesis involved a Florisil®-mediated reaction between azulene and paraformaldehyde. We investigated the generality of this process for the synthesis of calix[4]naphthalenes. The synthesis of calix[4]azulene was reproducible and provided us with a unique chance to look at an unfunctionalized "basket-like" molecule and its supramolecular complexation with C₆₀. The low solubility of calix[4]azulene also allowed us to use a unique method for the ¹H NMR and uv-vis spectroscopy studies. We report our methods and results in this thesis. These methods were then used to examine the stoichiometry of complexes formed between two different calix[n]arene with C₆₀.

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