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Title: Ene addition reactions involving jojoba bean oil, triglyceride vegetable oils and synthetic lubricant fluids
Author: McLellan, Jill Fraser
Awarding Body: University of Edinburgh
Current Institution: University of Edinburgh
Date of Award: 1995
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Ene addition reactions involving jojoba bean oil (a wax ester), sunflower oil (a triglyceride) and the synthetic fluids polyisobutene and polyalphaolefin have been investigated. Several enophiles have been employed, including azo compounds [diethyl azodicarboxylate (DEAD), 4-phenyl-1-1,2,4-triazoline-3,5-dione (PTAD) and 4-methyl-1,2,4-triazoline-3,5-dione (MTAD)], a sulfinyl compound [N-sulfinyl-p-toluenesulfonamide (TosNSO)] and formaldehyde. In order to investigate the scope of these reactions, and to gain spectral information for use in the analysis of more complex product mixtures, model alkenes were studied. For this purpose, methyl oleate, methyl elaidate and oleyl acetate were chosen, as were the symmetrical simple alkenes 3-hexene and 5-decene, and a series of terminal alkenes. In each case, identification and characterisation of addition products was achieved principally by NMR (IH and 13C) and FAB mass spectroscopy. Addition of the azo enophiles to jojoba oil and the mono-ene models resulted, in most cases, in the formation of adducts containing an alkene double bond with exclusively trans configuration. The exception to this was the addition of DEAD to 1-alkenes which resulted in adducts with ca. 20% of cis units. Where the lipid ene components were unsymmetrically substituted, the products were formed as 1:1 mixtures of regioisomers, as determined by high field 13C NMR spectroscopy. Kinetic measurements were made on the relative reactivities towards PTAD of methyl oleate, methyl elaidate, jojoba and trans-jojoba by two methods: using UV-visible spectroscopy to follow the consumption of the enophiles and secondly, by monitoring the relative rates of disappearance of lipid components by capillary gas chromatography. These measurements confirmed the visual observation that cis ene components reacted more quickly with PTAD than those with trans geometry. On reaction of the azo compounds with methyl linoleate, three major adduct types were isolated: non-conjugated dienes, conjugated dienes and diadducts resulting from a tandem ene/Diel-Alder cycloaddition. The ratio of these three adduct types was found to vary depending on the enophile. With the triazolines the non-conjugated dienes and tandem diadducts predominated while, conversely, for DEAD the conjugated dienes were the major products.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available