Oxygen and sulphur heterocycles derived from chloroaldehydes

Simple item page
dc.contributor.advisorIrving, H M N Hen_ZA
dc.contributor.authorArcher, Steven Jamesen_ZA
dc.date.accessioned2016-02-15T07:15:58Z
dc.date.available2016-02-15T07:15:58Z
dc.date.issued1984en_ZA
dc.descriptionIncludes bibliography.en_ZA
dc.description.abstractChloral may be trimerised, tetramised and polymerised, to form parachloral, metachloral and polychloral, respectively. Parachloral has two isomers: the cis-isomer and the trans-isomer. An analysis of the conformational equilibria occuring in solution, was carried out for trans-parachloral, using the techniques of dipole moment measurement and infrared and nmr spectroscopy Both isomers exist in cis-chair conformations, but differ in the chirality of the β-carbon atoms in the side chains. A comparison of the mass spectral fragmentations of parachloral and parabutylchloral is included. The structure of a related five-membered heterocycle, trans-chloralide was also investigated by x-ray crystallography. The cis-isomer of chloralide is reported for the first time. The unusual mechanism, in which carbon monoxide acts as nucleophile, by which chloralide is formed from chloral and fuming sulphuric acid, has been elucidated using 13C-labelling. The dehydrochlorination of chloralide under unexpected conditions, is also discussed. The isomerism in a series sulphur-containing analogues of parachloral was investigated. 2-Trans-dithioparachloral and its dehydrochlorination product, were shown by x-ray crystallography. A comparative study of the effects on the 1H and 13Cnmr spectra, of structural changes in these six-membered heterocycles, is discussed at length. Some introductory preparative work was done, regarding the potential use of 1,3,5-trithiane 1,3,5-trioxides with three axial sulphoxide groups, as terdentate ligands.en_ZA
dc.identifier.apacitationArcher, S. J. (1984). <i>Oxygen and sulphur heterocycles derived from chloroaldehydes</i>. (Thesis). University of Cape Town ,Faculty of Science ,Department of Chemistry. Retrieved from http://hdl.handle.net/11427/17043en_ZA
dc.identifier.chicagocitationArcher, Steven James. <i>"Oxygen and sulphur heterocycles derived from chloroaldehydes."</i> Thesis., University of Cape Town ,Faculty of Science ,Department of Chemistry, 1984. http://hdl.handle.net/11427/17043en_ZA
dc.identifier.citationArcher, S. 1984. Oxygen and sulphur heterocycles derived from chloroaldehydes. University of Cape Town.en_ZA
dc.identifier.ris TY - Thesis / Dissertation AU - Archer, Steven James AB - Chloral may be trimerised, tetramised and polymerised, to form parachloral, metachloral and polychloral, respectively. Parachloral has two isomers: the cis-isomer and the trans-isomer. An analysis of the conformational equilibria occuring in solution, was carried out for trans-parachloral, using the techniques of dipole moment measurement and infrared and nmr spectroscopy Both isomers exist in cis-chair conformations, but differ in the chirality of the β-carbon atoms in the side chains. A comparison of the mass spectral fragmentations of parachloral and parabutylchloral is included. The structure of a related five-membered heterocycle, trans-chloralide was also investigated by x-ray crystallography. The cis-isomer of chloralide is reported for the first time. The unusual mechanism, in which carbon monoxide acts as nucleophile, by which chloralide is formed from chloral and fuming sulphuric acid, has been elucidated using 13C-labelling. The dehydrochlorination of chloralide under unexpected conditions, is also discussed. The isomerism in a series sulphur-containing analogues of parachloral was investigated. 2-Trans-dithioparachloral and its dehydrochlorination product, were shown by x-ray crystallography. A comparative study of the effects on the 1H and 13Cnmr spectra, of structural changes in these six-membered heterocycles, is discussed at length. Some introductory preparative work was done, regarding the potential use of 1,3,5-trithiane 1,3,5-trioxides with three axial sulphoxide groups, as terdentate ligands. DA - 1984 DB - OpenUCT DP - University of Cape Town LK - https://open.uct.ac.za PB - University of Cape Town PY - 1984 T1 - Oxygen and sulphur heterocycles derived from chloroaldehydes TI - Oxygen and sulphur heterocycles derived from chloroaldehydes UR - http://hdl.handle.net/11427/17043 ER - en_ZA
dc.identifier.urihttp://hdl.handle.net/11427/17043
dc.identifier.vancouvercitationArcher SJ. Oxygen and sulphur heterocycles derived from chloroaldehydes. [Thesis]. University of Cape Town ,Faculty of Science ,Department of Chemistry, 1984 [cited yyyy month dd]. Available from: http://hdl.handle.net/11427/17043en_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.otherChemistryen_ZA
dc.titleOxygen and sulphur heterocycles derived from chloroaldehydesen_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
Files
Original bundle
Now showing 1 - 1 of 1
Thumbnail Image
Name:
thesis_sci_1984_archer_steven_james.pdf
Size:
3.69 MB
Format:
Adobe Portable Document Format
Description:
Download
Collections
PhD / Doctoral