Thesis (M.Sc.) -- University of Adelaide, Dept. of Organic Chemistry, 1971.

The application of various chromatographic technique to the mixed esters prepared from shellac has led to the discovery of ether-linked polymer fragments in shellac and the isolation and identification of a number of hitherto unrecognised aliphatic acids including saturated and unsaturated non-hydroxy acids, 6-keto-tetr'adecanoic acid, 6-hydroxytetradecanoic acid, 10-hydroxyhexadec-9-enoic acid, 16-hydroxyhexadecanoic acid, threo 9,10-dihydroxytetradecanoic acid. Appendix Lipolytic Studies of some Seed Oils containing Sterculic Acid. The sterculic acid containing seed oils, Eombacopsis glabra, Sterculia parviflora and Sterculia macrophylla, were examined and subjected to hydrolysis with pancreatic lipase.

Hydrolysis of lac resin yields a mixture of acids among which only two - aleuritic (up to 40%) and shellolio (up to 5%) - have been adequately characterised and examined by several investigators. The work embodied in this thesis represents some studies of the aliphatic acids in lac hydrolysate. The presence of a range of non-hydroxy acids (1.1%) 6-hydroxytetra- decanoic acid (not less than 8%), l6~hydroxyhexadecanoic acid and snother monohydroxyhexadecanoic acid has been demonstrated. The 6-hydroxytetradecanoic acid has been shown to be identical with butolic acid recently isolated by chemists of the Indian Lac Research Institute but considered by them to be a C1B hydroxy acid. The other acids have not previously been reported as constituents of lac resin. Reversed-phase chromatography was found to be unsuitable for the examination of lac acids, probably due to their highly hydroxylated nature. Dehydroxylation experiments on lac acids by lodlnatlon- deiodination and by bromination-debrominatlon revealed the presence of hydroxylated tetradecanoic and hexadecanoic acids; brominatlon- debrominatlon reactions also showed the presence of small amounts of vicinal dihydroxy acids of these two series. Partition of lac acids between petroleum ether and 80% aqueous methanol and subsequent examination of the petroleum other-soluble material (1.1%) revealed the presence of dodecanoic (trace). tetradec-9-onoic and tetradecanoic acids (25%), hexadec-9-enoic acid (13%), hexadecanoic acid (53%), octadec-9-enoic acid (7%) and octadecanoic acid (2%). Examination of lac acids by adsorption, gas-liquid and thin layer chromatography showed the presence of 6-hydroxy-tetradecanoic acid (8% or more of lac acids), 16-hydroxy-hexadeoanoic acid and another monohydroxyhexadeoanoic acid.

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This research has been directed at the study of facilitated oxidation of aliphatic sulfides by neighboring group participation. Mesocyclic polythioether and 2-substituted 6-methylthiobicyclo[2.2.1]heptane derivatives have been examined as model compounds for biological redox reactions. The preparations, structural analogues, and oxidation studies of such compounds have been investigated. A new technique has been developed for the preparation of mesocyclic polythioethers. Conformational analysis, both gas phase and solid state, and quantum mechanical analysis of one- and two-electron oxidation of mesocyclic polythioethers have been undertaken. Crystal and molecular structures of some transition metal complexes of 1,4,7-trithiacyclononane, as well as a number of 2-substituted 6-methylthiobicyclo[2.2.1]heptane derivatives have been determined using single crystal X-ray techniques. Stereoselective oxidation of 2-endo-(hydroxymethyl)-6- endo(methylthio)bicyclo[2.2.1]heptane has been achieved leading to both corresponding diastereomeric sulfoxides.