Synthetic investigations on new calixsalens and modified thiacalixarenes
Thesis (Ph.D.)--Memorial University of Newfoundland, 2008. Chemistry Includes bibliographical references (leaves 229-234) "Calix"-compounds have "cup"- or "basket"-like shapes which make them attractive synthetic targets for host-guest studies and for many other potenti...
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ftmemorialunivdc:oai:collections.mun.ca:theses4/94120 2023-05-15T17:23:33+02:00 Synthetic investigations on new calixsalens and modified thiacalixarenes Habashneh, Almeqdad, 1973- Memorial University of Newfoundland. Dept. of Chemistry 2008 xx, 250 leaves : ill. (some col.) Image/jpeg; Application/pdf http://collections.mun.ca/cdm/ref/collection/theses4/id/94120 Eng eng Electronic Theses and Dissertations (23.16 MB) -- http://collections.mun.ca/PDFs/theses/Habashneh_Almeqdad.pdf a2701081 http://collections.mun.ca/cdm/ref/collection/theses4/id/94120 The author retains copyright ownership and moral rights in this thesis. Neither the thesis nor substantial extracts from it may be printed or otherwise reproduced without the author's permission. Paper copy kept in the Centre for Newfoundland Studies, Memorial University Libraries Macrocyclic compounds--Synthesis Substitution reactions Text Electronic thesis or dissertation 2008 ftmemorialunivdc 2015-08-06T19:22:11Z Thesis (Ph.D.)--Memorial University of Newfoundland, 2008. Chemistry Includes bibliographical references (leaves 229-234) "Calix"-compounds have "cup"- or "basket"-like shapes which make them attractive synthetic targets for host-guest studies and for many other potential applications. The research described in this thesis deals with two sets of objectives, (a) The synthesis and characterization of new generation of calixsalens; and (b) The study of the reactions of thiacalix[4]arene 1,3-bistriflate and the chemistry of thiacalix[2]phenoxathiins. -- Calixsalens are dimeric compounds in which the two salen units are connected by methylene, ethylene or sulfonyl linking groups, and are usually prepared under Schiff-base macrocyclizations of bis-salicylaldehydes with diamines. Chiral Mn(III)-calixsalen complexes have been designed to serve as enantioselective epoxidation catalysts which act via a host-guest catalytic mechanism in which reactants can be included within the chiral cavities of the new complexes. New calixsalen ligands with large (chiral) cavities were synthesized by incorporating new linking groups between the two salen units. Modified low moi% Pd Suzuki conditions efficiently produced the desired targeted bis-salicylaldehydes which were used as the precursors for the desired calixsalen compounds. -- The second part of this thesis describes the attempted modification of thiacalix[4]arene to form the narrow rim-functionalized arylethynyl derivative, using the Sonogashira reaction. However, the reactions employed produced instead an unexpected new pheoxathiin product under Cu(I)-catalyzed conditions. A host-guest complexation study was conducted with the new phenoxathiin and its de-tert-butylated analogue and both were shown to be moderate receptors for Ag⁺ and Hg²⁺ ions but not at all with the neutral C₆₀ and C₇₀ fullerenes. Thesis Newfoundland studies University of Newfoundland Memorial University of Newfoundland: Digital Archives Initiative (DAI) |
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Memorial University of Newfoundland: Digital Archives Initiative (DAI) |
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English |
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Macrocyclic compounds--Synthesis Substitution reactions |
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Macrocyclic compounds--Synthesis Substitution reactions Habashneh, Almeqdad, 1973- Synthetic investigations on new calixsalens and modified thiacalixarenes |
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Macrocyclic compounds--Synthesis Substitution reactions |
description |
Thesis (Ph.D.)--Memorial University of Newfoundland, 2008. Chemistry Includes bibliographical references (leaves 229-234) "Calix"-compounds have "cup"- or "basket"-like shapes which make them attractive synthetic targets for host-guest studies and for many other potential applications. The research described in this thesis deals with two sets of objectives, (a) The synthesis and characterization of new generation of calixsalens; and (b) The study of the reactions of thiacalix[4]arene 1,3-bistriflate and the chemistry of thiacalix[2]phenoxathiins. -- Calixsalens are dimeric compounds in which the two salen units are connected by methylene, ethylene or sulfonyl linking groups, and are usually prepared under Schiff-base macrocyclizations of bis-salicylaldehydes with diamines. Chiral Mn(III)-calixsalen complexes have been designed to serve as enantioselective epoxidation catalysts which act via a host-guest catalytic mechanism in which reactants can be included within the chiral cavities of the new complexes. New calixsalen ligands with large (chiral) cavities were synthesized by incorporating new linking groups between the two salen units. Modified low moi% Pd Suzuki conditions efficiently produced the desired targeted bis-salicylaldehydes which were used as the precursors for the desired calixsalen compounds. -- The second part of this thesis describes the attempted modification of thiacalix[4]arene to form the narrow rim-functionalized arylethynyl derivative, using the Sonogashira reaction. However, the reactions employed produced instead an unexpected new pheoxathiin product under Cu(I)-catalyzed conditions. A host-guest complexation study was conducted with the new phenoxathiin and its de-tert-butylated analogue and both were shown to be moderate receptors for Ag⁺ and Hg²⁺ ions but not at all with the neutral C₆₀ and C₇₀ fullerenes. |
author2 |
Memorial University of Newfoundland. Dept. of Chemistry |
format |
Thesis |
author |
Habashneh, Almeqdad, 1973- |
author_facet |
Habashneh, Almeqdad, 1973- |
author_sort |
Habashneh, Almeqdad, 1973- |
title |
Synthetic investigations on new calixsalens and modified thiacalixarenes |
title_short |
Synthetic investigations on new calixsalens and modified thiacalixarenes |
title_full |
Synthetic investigations on new calixsalens and modified thiacalixarenes |
title_fullStr |
Synthetic investigations on new calixsalens and modified thiacalixarenes |
title_full_unstemmed |
Synthetic investigations on new calixsalens and modified thiacalixarenes |
title_sort |
synthetic investigations on new calixsalens and modified thiacalixarenes |
publishDate |
2008 |
url |
http://collections.mun.ca/cdm/ref/collection/theses4/id/94120 |
genre |
Newfoundland studies University of Newfoundland |
genre_facet |
Newfoundland studies University of Newfoundland |
op_source |
Paper copy kept in the Centre for Newfoundland Studies, Memorial University Libraries |
op_relation |
Electronic Theses and Dissertations (23.16 MB) -- http://collections.mun.ca/PDFs/theses/Habashneh_Almeqdad.pdf a2701081 http://collections.mun.ca/cdm/ref/collection/theses4/id/94120 |
op_rights |
The author retains copyright ownership and moral rights in this thesis. Neither the thesis nor substantial extracts from it may be printed or otherwise reproduced without the author's permission. |
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