Al-Saraierh, Hassan (2007) Synthesis of new Calixarenes and Calixnaphthalenes via Sonogashira reactions, photochemically-induced reactions and [2+2] fragment condensation reactions. Doctoral (PhD) thesis, Memorial University of Newfoundland.
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Calixarenes are macrocyclic compounds which can be produced with different sizes and functionalities. They are mainly synthesized by 'one-pot' base-induced condensation reactions of the corresponding phenol(s) with paraformaldehyde. For example, the most accessible and commonly-used calixarene, tetra-p-tert-butylcalixarene is produced by such a reaction, of p-tertbutylphenol with para-formaldehyde. The well-defined "calix"- or "cup"-like shape in most of these compounds have made them attractive targets for host-guest and/or supramolecular studies and many other applications. -- The work described in this thesis concerns the synthesis and a study of the properties of some new modified calixarenes and calixnaphthalenes which were synthesized using different methods. Among the topics dealt with are the following: (a) An attempt to develop a new methodology for the wide-rim modification of calixnaphthalene by using a suitably pre-functionalized precursor. (b) The synthesis of a new thiophene-based calixarene using [2+2] fragment condensation reactions. (c) The synthesis of a new member of the homooxacalixnaphthalene family using [2+2] fragment condensation reactions. (d) The ability to modify the dimensions of the cavity of a calixnaphthalene by extending the bridging units with (-CH₂-CH₂-) and/or (-CH₂-O-CH₂-) groups. -- The narrow-rim hydroxyl groups of calixarenes are known to be resistant to substitution displacement. The Sonogashira coupling reaction with trimethylsilylacetylene and phenylacetylene, however, has now been extended to trimethylsilylacetylene and phenylacetylene, however, has now been extended to the bistriflate of p-tert-butylcalixarene, previously known to be resistant to Stille, Neigishi, or Suzuki-Miyaura reactions. Under some of the reaction conditions investigated, the previously unknown narrow-rim mono- and diiodo-p-tert-butylcalixarene products were also produced, in addition to the targeted narrow-rim mono- and dialkynyl products. Homocoupling of the narrow rim monoethynyl-p-tert-butyl-calixarene produced a new narrow-rim rigid butadiyne-linked bis-p-tert-butylcalix[4 ]arene. -- Finally, the syntheses of several new donor-acceptor narrow-rim functionalized alkynylcalixarenes, and their potential in nonlinear optical materials are described.
|Item Type:||Thesis (Doctoral (PhD))|
|Additional Information:||Includes bibliographical references.|
|Department(s):||Science, Faculty of > Chemistry|
|Library of Congress Subject Heading:||Calixarenes--Synthesis; Chemical reactions; Naphthalenes--Synthesis.|
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