Synthesis and characterization of macrocyclic naphthalene ring-based calix[n]arenes, lactones and amides

Al Hujran, Tayel (2012) Synthesis and characterization of macrocyclic naphthalene ring-based calix[n]arenes, lactones and amides. Doctoral (PhD) thesis, Memorial University of Newfoundland.

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Abstract

The work described in this thesis is concerned mainly with the synthesis of some new molecular receptors which are naphthalene ring-based calixarenes, lactones and amide macrocycles. Their complexation properties with fullerenes C₆₀ and/or cationic guests such as tetramethylammonium acetate and/or alkali metal cations were studied. -- In Chapter 2, the syntheses of the macrocycle lactones and their clathrates are described. The structures of these macrocycles were determined by X-ray analysis which revealed that they formed either cage or channel-type clathrates when crystallized from different solvents. -- The work described in the Chapter 3 concerns the synthesis of a series of new di- and tetraamide macrocycles, respectively, from the [1+1] and [2+2] fragment cyclocondensation reactions of 4,4'-methylenebis(3-methoxy-2-naphthoyl chloride) and its derivatives with 1,8-diamino-3,6-dioxaoctane or with 1,10-diamino-4,7-dioxadecane. -- In Chapter 4, synthetic studies are described toward unprecedented acenaphthene, ring-based calixarene analogues, which could serve as wider and deeper bowl-shaped cavity-containing molecular receptors. The syntheses of homooxacalix[4]acenaphthene was achieved using a [2+2] fragment condensation strategy. Its X-ray structure showed the macrocycle in an 1,3-alternate conformation. As determined by ¹H-NMR spectroscopy, homooxacalix[4]acenaphthene was found to be a moderately good host for complexation with C₆₀ in toluene-d₈ solution. -- In Chapter 5 a series of new mixed naphthalene ring-based homooxacalix[4]arenes were synthesized also by employing a [2+2]-type fragment condensation reaction. X-ray structures of octahomotetraoxacalix[2]naphthalene[2]pyridine crystals grown from two different solvent systems revealed that the structures adopted 1,3-alternate and cone conformations. ¹H-NMR titration studies for this macrocycle revealed it to be a good host for binding TMAA in CDC1₃ solution in 1:1 ratio.

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