A structure-reactivity study of selected phosphate esters

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dc.contributor.advisorNassimbeni, Luigi Ren_ZA
dc.contributor.authorBond, Dianne Ruthen_ZA
dc.date.accessioned2016-11-14T06:55:50Z
dc.date.available2016-11-14T06:55:50Z
dc.date.issued1985en_ZA
dc.descriptionBibliography: pages 201-208.en_ZA
dc.description.abstractA 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.en_ZA
dc.identifier.apacitationBond, D. R. (1985). <i>A structure-reactivity study of selected phosphate esters</i>. (Thesis). University of Cape Town ,Faculty of Science ,Department of Chemistry. Retrieved from http://hdl.handle.net/11427/22521en_ZA
dc.identifier.chicagocitationBond, Dianne Ruth. <i>"A structure-reactivity study of selected phosphate esters."</i> Thesis., University of Cape Town ,Faculty of Science ,Department of Chemistry, 1985. http://hdl.handle.net/11427/22521en_ZA
dc.identifier.citationBond, D. 1985. A structure-reactivity study of selected phosphate esters. University of Cape Town.en_ZA
dc.identifier.ris TY - Thesis / Dissertation AU - Bond, Dianne Ruth AB - 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. DA - 1985 DB - OpenUCT DP - University of Cape Town LK - https://open.uct.ac.za PB - University of Cape Town PY - 1985 T1 - A structure-reactivity study of selected phosphate esters TI - A structure-reactivity study of selected phosphate esters UR - http://hdl.handle.net/11427/22521 ER - en_ZA
dc.identifier.urihttp://hdl.handle.net/11427/22521
dc.identifier.vancouvercitationBond DR. A structure-reactivity study of selected phosphate esters. [Thesis]. University of Cape Town ,Faculty of Science ,Department of Chemistry, 1985 [cited yyyy month dd]. Available from: http://hdl.handle.net/11427/22521en_ZA
dc.language.isoengen_ZA
dc.publisher.departmentDepartment of Chemistryen_ZA
dc.publisher.facultyFaculty of Scienceen_ZA
dc.publisher.institutionUniversity of Cape Town
dc.subject.otherPhysical Chemistryen_ZA
dc.subject.otherChemistryen_ZA
dc.titleA structure-reactivity study of selected phosphate estersen_ZA
dc.typeDoctoral Thesis
dc.type.qualificationlevelDoctoral
dc.type.qualificationnamePhDen_ZA
uct.type.filetypeText
uct.type.filetypeImage
uct.type.publicationResearchen_ZA
uct.type.resourceThesisen_ZA
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