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A structure-reactivity study of selected phosphate esters
Bibliography: pages 201-208.
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| Main Author: | |
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| Other Authors: | |
| Format: | Thesis |
| Language: | English |
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Department of Chemistry
2016
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| _version_ | 1867614207282774016 |
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| access_status_str | Open Access |
| author | Bond, Dianne Ruth |
| author2 | Nassimbeni, Luigi R |
| author_browse | Bond, Dianne Ruth Nassimbeni, Luigi R |
| author_facet | Nassimbeni, Luigi R Bond, Dianne Ruth |
| author_sort | Bond, Dianne Ruth |
| collection | Thesis |
| description | Bibliography: pages 201-208. |
| format | Thesis |
| id | oai:open.uct.ac.za:11427/22521 |
| institution | University of Cape Town (South Africa) |
| language | eng |
| last_indexed | 2026-06-10T12:48:22.440Z |
| license_str | Not specified — see source repository |
| provenance_str_mv | Harvested via OAI-PMH from UCTD — University of Cape Town Open Access Repository |
| publishDate | 2016 |
| publishDateRange | 2016 |
| publishDateSort | 2016 |
| publisher | Department of Chemistry |
| publisherStr | Department of Chemistry |
| record_format | dspace |
| source_str | UCTD — University of Cape Town Open Access Repository |
| spelling | oai:open.uct.ac.za:11427/22521 A structure-reactivity study of selected phosphate esters Bond, Dianne Ruth Nassimbeni, Luigi R Physical Chemistry Chemistry Bibliography: pages 201-208. A comparative X-ray analysis study of bis(4-nitrophenyl)-8-quinolinyl phosphate (4), 1-naphthyl-bis(4-nitrophenyl) phosphate (5) and 4-nitrophenyl -8-quinolinyl phosphate (5) was undertaken. In compound (4) donor-acceptor nitrogen-phosphorus interactions change the geometry of the molecule from tetrahedral to quasi trigonal bipyramidal, thus the structure may be considered as an "early stage" of the intramolecular displacement of the 4-ni trophenoxide group. In the diester (6) this interaction is replaced by intermolecular N+ -H...O- hydrogen bonding. In addition the intramolecular non-bonded potential energies of (4) and (5) were calculated and the minimum-energy conformations were compared with those determined by X-ray diffraction. These results confirm the differences observed in the intramolecular interactions operative in (4) and (5). The mass spectra of (4) and (5) are dramatically different with respect to the fragmentation involving expulsion of the 4-nitrophenoxy radical and formation of the corresponding phosphorylitum ion by nitrogen participation. Rate measurements for the base-catalysed hydrolysis of the first P-OPNP linkage show that (4) is not significantly more reactive than (5) and provide no evidence for intramolecular nucleophilic catalysis in the hydrolysis of (4). The crystal and molecular structure of 1-naphthyl acetate (7) was determined. Attempts to grow suitable crystals of 8-quinolinyl acetate (8) failed and therefore its structure could not be elucidated. Possible intramolecular nitrogen - carbonyl carbon interactions operative in (8) could therefore not be established. 2016-11-14T06:55:50Z 2016-11-14T06:55:50Z 1985 Doctoral Thesis Doctoral PhD http://hdl.handle.net/11427/22521 eng application/pdf Department of Chemistry Faculty of Science University of Cape Town |
| spellingShingle | Physical Chemistry Chemistry Bond, Dianne Ruth A structure-reactivity study of selected phosphate esters |
| thesis_degree_str | Doctoral |
| title | A structure-reactivity study of selected phosphate esters |
| title_full | A structure-reactivity study of selected phosphate esters |
| title_fullStr | A structure-reactivity study of selected phosphate esters |
| title_full_unstemmed | A structure-reactivity study of selected phosphate esters |
| title_short | A structure-reactivity study of selected phosphate esters |
| title_sort | structure reactivity study of selected phosphate esters |
| topic | Physical Chemistry Chemistry |
| url | http://hdl.handle.net/11427/22521 |
| work_keys_str_mv | AT bonddianneruth astructurereactivitystudyofselectedphosphateesters AT bonddianneruth structurereactivitystudyofselectedphosphateesters |