Synthesis of nitrogen analogues of ecdysones

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dc.contributor.advisor Cambie, R. C. en
dc.contributor.author Potter, Graeme John en
dc.date.accessioned 2007-08-18T10:17:05Z en
dc.date.available 2007-08-18T10:17:05Z en
dc.date.issued 1978 en
dc.identifier THESIS 79-070 en
dc.identifier.citation Thesis (PhD--Chemistry)--University of Auckland, 1978 en
dc.identifier.uri http://hdl.handle.net/2292/1471 en
dc.description Full text is available to authenticated members of The University of Auckland only. en
dc.description.abstract This thesis is concerned with the utilization of the steroidal alkaloid solasodine (23) as a nitrogen-containing ecdysone precursor. Studies were also directed towards the preparation of nitrogen-containing ecdysone analogues from crustecdysone (8) and cholesterol (5). Preliminary synthetic studies revealed the necessity for initial protection of the secondary amino function of solasodine. It was found that acetylation of this substrate under a variety of basic conditions gave in each instance a mixture of the O,N-diacetate (34) and the isomeric Δ20(22)- and Δ22(23)-enamine triacetates (39). These latter compounds were formed as a result of ring-chain tautomerism of the spiroaminoketal moiety of solasodine. Modification of the acetylation products was studied in an effort to introduce the required ecdysone functionality. Synthetic approaches utilizing solasodine-O,N-ditosylate (35) were also investigated. These involved epoxidation, elimination, and solvolyses. The 13C n.m.r. spectra of a number of solasodine derivatives have been assigned. Oxidative cleavage of crustecdysone under a variety of conditions was investigated; best results were obtained with Jones reagent. The 2,3-glycol grouping of the resultant diketone (12) was protected as the isopropylidene and nitrogen was introduced into this compound in the form of a C-20 oxime. Proposed transformations of the oxime are suggested. Nitrogen was introduced into the nucleus of a cholestane derivative as a 2α,3α-hydroxy ρ-toluenesulphonamide. The technique of preparative HPLC was used to advantage during the above work and aspects of the technique are discussed. en
dc.language.iso en en
dc.publisher ResearchSpace@Auckland en
dc.relation.ispartof PhD Thesis - University of Auckland en
dc.relation.isreferencedby UoA9921846514002091 en
dc.rights Restricted Item. Available to authenticated members of The University of Auckland. en
dc.rights.uri https://researchspace.auckland.ac.nz/docs/uoa-docs/rights.htm en
dc.title Synthesis of nitrogen analogues of ecdysones en
dc.type Thesis en
thesis.degree.discipline Chemistry en
thesis.degree.grantor The University of Auckland en
thesis.degree.level Doctoral en
thesis.degree.name PhD en
dc.rights.holder Copyright: The author en


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