{"id":{"repo_id":"auckland-ms","oai_identifier":"oai:researchspace.auckland.ac.nz:2292/2484"},"canonical_url":"https://search.dev.ndltd.org/etd/auckland-ms/oai:researchspace.auckland.ac.nz:2292/2484","repository":{"repo_id":"auckland-ms","name":"University of Auckland","base_url":"https://researchspace.auckland.ac.nz/server/oai/request"},"display":{"title":"Oxidation of Ring-A Aromatic Steroids","abstract":"This thesis is concerned with a study of the oxidation of ring-A aromatic steroids using either chromium trioxide-aqueous sulphuric acid-acetone or chromium trioxide-aqueous acetic acid mixtures. It was found that chromic acid oxidation of ring-A aromatic steroids substituted with a strong electron-donating group, gives rise to products with the site of oxidation being predominantly that para to the activating group. Thus C-3 methoxy ring-A aromatic steroids give the corresponding 9b-hydroxy-11-oxo and 9-oxo-9,11-seco-11-oic acid derivatives as the major products and the 6-oxo derivative as a minor oxidation product. However, a ketol was not formed if a C-3 methoxy ring-A aromatic steroid also contained a substituent at C-1. The C-1-methoxy-4-methyl ring-A aromatic steroids give the 4-carboxy derivative as the major product and again the 6-oxo compound as a minor neutral product. The acetoxy and methyl substituted ring-A aromatic steroids, however, all give rise to the 6-oxo derivatives as the major products. The usual oxidation product of a ring-A aromatic steroid is therefore the 6-oxo product unless it is substituted with a methoxy group in a position which will stabilise an electron deficiency at a site other than C-6. Oxidation will then occur predominantly at the stabilised site unless it is sterically blocked.","abstract_html":"This thesis is concerned with a study of the oxidation of ring-A aromatic steroids using either chromium trioxide-aqueous sulphuric acid-acetone or chromium trioxide-aqueous acetic acid mixtures. It was found that chromic acid oxidation of ring-A aromatic steroids substituted with a strong electron-donating group, gives rise to products with the site of oxidation being predominantly that para to the activating group. Thus C-3 methoxy ring-A aromatic steroids give the corresponding 9b-hydroxy-11-oxo and 9-oxo-9,11-seco-11-oic acid derivatives as the major products and the 6-oxo derivative as a minor oxidation product. However, a ketol was not formed if a C-3 methoxy ring-A aromatic steroid also contained a substituent at C-1. The C-1-methoxy-4-methyl ring-A aromatic steroids give the 4-carboxy derivative as the major product and again the 6-oxo compound as a minor neutral product. The acetoxy and methyl substituted ring-A aromatic steroids, however, all give rise to the 6-oxo derivatives as the major products. The usual oxidation product of a ring-A aromatic steroid is therefore the 6-oxo product unless it is substituted with a methoxy group in a position which will stabilise an electron deficiency at a site other than C-6. Oxidation will then occur predominantly at the stabilised site unless it is sterically blocked.","abstract_has_math":false,"creators":["Carlisle, Valerie F."],"institution":"ResearchSpace@Auckland","degree_name":"PhD","degree_level":"Doctoral","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":1969,"date_issued":"1969","date_published":"1969","updated_at":"2026-07-24T01:07:07Z","subjects":[],"languages":["en"],"rights":["Items in ResearchSpace are protected by copyright, with all rights reserved, unless otherwise indicated."],"rights_urls":["https://researchspace.auckland.ac.nz/docs/uoa-docs/rights.htm"],"identifier_entries":[]},"links":{"outbound_url":"https://hdl.handle.net/2292/2484","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["Carlisle, Valerie F."]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2008-04-10T22:39:29Z"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2008-04-10T22:39:29Z"]},{"key":"dc:date.issued","label":"Date","values":["1969"]},{"key":"dc:publisher","label":"Institution","values":["ResearchSpace@Auckland"]},{"key":"dc:relation.isreferencedby","label":"Dc Relation Isreferencedby","values":["UoA216070"]},{"key":"dc:type","label":"Dc Type","values":["Thesis"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry"]},{"key":"thesis:degree_level","label":"Degree Level","values":["Doctoral"]},{"key":"thesis:degree_name","label":"Degree Name","values":["PhD"]},{"key":"thesis:institution_name","label":"Thesis Institution Name","values":["The University of Auckland"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language.iso","label":"Language (ISO)","values":["en"]},{"key":"dc:rights","label":"Dc Rights","values":["Items in ResearchSpace are protected by copyright, with all rights reserved, unless otherwise indicated."]},{"key":"dc:rights.uri","label":"Rights URI","values":["https://researchspace.auckland.ac.nz/docs/uoa-docs/rights.htm"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["https://hdl.handle.net/2292/2484"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["This thesis is concerned with a study of the oxidation of ring-A aromatic steroids using either chromium trioxide-aqueous sulphuric acid-acetone or chromium trioxide-aqueous acetic acid mixtures. It was found that chromic acid oxidation of ring-A aromatic steroids substituted with a strong electron-donating group, gives rise to products with the site of oxidation being predominantly that para to the activating group. Thus C-3 methoxy ring-A aromatic steroids give the corresponding 9b-hydroxy-11-oxo and 9-oxo-9,11-seco-11-oic acid derivatives as the major products and the 6-oxo derivative as a minor oxidation product. However, a ketol was not formed if a C-3 methoxy ring-A aromatic steroid also contained a substituent at C-1. The C-1-methoxy-4-methyl ring-A aromatic steroids give the 4-carboxy derivative as the major product and again the 6-oxo compound as a minor neutral product. The acetoxy and methyl substituted ring-A aromatic steroids, however, all give rise to the 6-oxo derivatives as the major products. The usual oxidation product of a ring-A aromatic steroid is therefore the 6-oxo product unless it is substituted with a methoxy group in a position which will stabilise an electron deficiency at a site other than C-6. Oxidation will then occur predominantly at the stabilised site unless it is sterically blocked."]},{"key":"dc:title","label":"Title","values":["Oxidation of Ring-A Aromatic Steroids"]}]}],"canonical_facts":{"dc:creator":["Carlisle, Valerie F."],"dc:date.accessioned":["2008-04-10T22:39:29Z"],"dc:date.available":["2008-04-10T22:39:29Z"],"dc:date.issued":["1969"],"dc:description.abstract":["This thesis is concerned with a study of the oxidation of ring-A aromatic steroids using either chromium trioxide-aqueous sulphuric acid-acetone or chromium trioxide-aqueous acetic acid mixtures. It was found that chromic acid oxidation of ring-A aromatic steroids substituted with a strong electron-donating group, gives rise to products with the site of oxidation being predominantly that para to the activating group. Thus C-3 methoxy ring-A aromatic steroids give the corresponding 9b-hydroxy-11-oxo and 9-oxo-9,11-seco-11-oic acid derivatives as the major products and the 6-oxo derivative as a minor oxidation product. However, a ketol was not formed if a C-3 methoxy ring-A aromatic steroid also contained a substituent at C-1. The C-1-methoxy-4-methyl ring-A aromatic steroids give the 4-carboxy derivative as the major product and again the 6-oxo compound as a minor neutral product. The acetoxy and methyl substituted ring-A aromatic steroids, however, all give rise to the 6-oxo derivatives as the major products. The usual oxidation product of a ring-A aromatic steroid is therefore the 6-oxo product unless it is substituted with a methoxy group in a position which will stabilise an electron deficiency at a site other than C-6. Oxidation will then occur predominantly at the stabilised site unless it is sterically blocked."],"dc:identifier.uri":["https://hdl.handle.net/2292/2484"],"dc:language.iso":["en"],"dc:publisher":["ResearchSpace@Auckland"],"dc:relation.isreferencedby":["UoA216070"],"dc:rights":["Items in ResearchSpace are protected by copyright, with all rights reserved, unless otherwise indicated."],"dc:rights.uri":["https://researchspace.auckland.ac.nz/docs/uoa-docs/rights.htm"],"dc:title":["Oxidation of Ring-A Aromatic Steroids"],"dc:type":["Thesis"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["Doctoral"],"thesis:degree_name":["PhD"],"thesis:institution_name":["The University of Auckland"]},"updated_at":"2026-07-24T01:07:07Z"}