Synthesis of flavan-3, 4-diols, stereochemistry of novel biflavanols and new non-tannins from Acacia Mearnsii
- Authors: Saayman, Henry Martin
- Date: 1967
- Subjects: Tannins Acacia mearnsii Stereochemistry Wattles (Plants) Chemistry, Analytic
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4444 , http://hdl.handle.net/10962/d1007704
- Description: From Summary: The structural elucidation of condensed tannins, which are considered to consist of C₁₅-flavan units, presents certain difficulties. These tannins occur in extremely complex mixtures, and their isolation is complicated by their susceptibility to oxidative denaturation. Limitations in the formation of significant degradation products add to these problems. Since condensed tannins of black wattle bark yield anthocyanidins on treatment with mineral acids, they are considered to be proanthocyanidin in character. For this reason the initial approach to the investigation of the structures of condensed tannins was by way of the synthesis of novel 7-hydroxyflavan-3,4-diols having a low degree of hydroxyl substitution. Submission of these to modern physical techniques such as nuclear magnetic resonance (n.m.r.) spectroscopy would yield valuable data regarding the chemical shifts and coupling constants of heterocyclic and benzenoid protons which may be used for subsequent work on more highly hydroxylated diols, biflavanols and finally the condensed tannins themselves.
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- Date Issued: 1967
An investigation of the orientation of certain long-chain fatty acids at the air-water interface
- Authors: Saayman, Henry Martin
- Date: 1962
- Subjects: Fatty acids , Surface chemistry
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4496 , http://hdl.handle.net/10962/d1013117
- Description: The results obtained for the cross-sectional areas of the series of long-chain fatty acids may best be summarized with the aid of Graph 9. This graphical representation of the molecular areas, in Ų , against the chain length (n), of the fatty acid molecules, illustrates variation of the areas with chain length for the series in recrystallized form, and also for selected samples in the zone purified and vacuum distilled forms. On the graph, the limits of variation of the molecular areas have been represented as lines of a length corresponding to twice the standard deviation (2S). This is to give representation that the standard deviation may be positive or negative in relation to the mean. For molecules with n odd and lying between 15 and 19, the molecular area decreases. This may be due to the effect of 3 factorsg (1) A general decrease in lateral translation because of the increasing molecular mass (translational kinetic energy per molecule = ½ mc ⁻²), resulting in closer spacing of molecules. (2) A general, but steady decrease in the angle of tilt of the molecules which thus tend to be held more erect in the condensed film. (3) A general decrease in the precessional motion of the hydrophobic chain groups. For molecules with n odd and between 19 and 23, the molecular areas increase probably due to the steady increase in molecular mass causing the long chains to commence to buckle, tilt or topple in their upper regions. This tilting becomes greater because of the increasing gravitational effect on the heavier molecules which tends to make them assume a flatter posture in relation to the surface. The lower values observed for margaric and nonadecanoic acids, may be due to increasing symmetry in the chain, with corresponding economy in packing in condensed monolayers. This effect may be connected with increasing cylindrical symmetry of the hydrocarbon chain for even values of n. The results of this investigution, incomplete as it is, - serve to indicate what might reasonably be expected to happen in the orientation of these fatty acids in monolayers. Further work, especially on a greater range of acids with even n, is clearly necessary in order to establish the tentative ideas which have been suggested. However, in the present research, work was limited to those acids in the series which were obtainable without undue difficulty or delay, those which would spread readily under the conditions of experiments carried out at 20°C, and those which could be purified relatively easily. The acids below n = 15 in the series were found to be too soluble in aqueous substrates, at operating temperatures of 20°C, to yield reliable evidence with the Langmuir trough technique. The acids above n = 23 were unobtainable commercially and the synthesis of those acids from the lower members in the series presented problems of isolating the required specimens and difficulty in purifying these, which were considered b be beyond the scope of the present research. Summary and conclusion, p. 122.
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- Date Issued: 1962