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Title: Synthesis and solution chemistry of functional surfactants
Author: Griggs, Colin George
ISNI:       0000 0001 3520 7923
Awarding Body: University of Oxford
Current Institution: University of Oxford
Date of Award: 1979
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A number of synthetic approaches to preparing a metal-binding surfactant, containing the α-dioxime moiety, are described. Both linear and convergent synthetic methods have been unsuccessful in the preparation of a target surfactant. While the preparation of such a target molecule was not realised, some simple long chain α-dioximes have however been prepared in the course of investigating various synthetic methods. Microemulsion phenomena of these simple α-dioximes in aqueous surfactant micelles have been investigated by ultrasonic techniques, with the kinetics associated with such a process being determined. The kinetics of such α-dioximes in a co-micellar environment with nickel ions has been investigated under various conditions e.g. pH, surfactant concentration, and are reported. In order to prepare chiral functionalised long-chain surfactants of known configuration via "directed resolution" of diasteromeric amides obtained from racemic lactones, the alkylation of lactone enolates has been investigated. Only the enolate of γ-butyrolactone has been satisfactorily alkylated with long-chain electrophiles. Numerous attempts to alkylate the enolate of ε-caprolactone have been uniformly unsuccessful. Through optimisation of conditions a viable synthesis to α-alkylated derivatives of γ-butyrolactone has been found. "Directed resolution" of diastereomeric amides, prepared from the racemic γ-butyrolactone derivatives, have resulted in the isolation of optically pure lactones. Investigation of potential protecting groups for the α-diketone moiety in a functional surfactant synthesis resulted in the preparation of a 9,10-dimethyl substituted 1,4,5,8-tetraoxadecalin in a model study. Analysis of the AA′ BB′ multiplet couplings provided unambiguous evidence that the structure of this bicyclic molecule has the cis-configuration. Activation parameters for the ring inversion process between enantiomeric forms were obtained by line shape analysis of the variable temperature 1H- and 13C-n.m.r. spectra.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available