The rates of hydrolysis of model sulphonate esters in aqueous solutions of concentrated sulphuric acid were studied. Data for these compounds were used to calculate the solvent parameters Y<SUB>OTs</SUB> and N<SUB>OTs</SUB> in 0-60% w/w sulphuric acid using the Grunwald-Winstein approach. The small increases in hydrolysis rates of sulphonate esters were found to be due to medium effects with no acid catalysis occurring below 50% w/w sulphuric acid. The product distribution of 6-octyn-2-ol benzene sulphonates were predicted from Y<SUB>OTs</SUB> and N<SUB>OTs</SUB> parameters in sulphuric acid solution. Phosphonate esters were found to be sensitive to acid catalysis in dilute acid solution. Phosphonate rate data in dilute acid solution were dissected into the contributions arising from solvolytic and acid-catalysed reaction pathways. The rates of hydrolyses of phosphonate esters in 0-98% w/w sulphuric acid solution were measured and discussed in terms of acidity function theory. A novel approach, using an extension of the Grunwald-Winstein method, to correlate reaction kinetics of protonated substrates in concentrated acid solution was developed. The similarities between this novel approach and the more traditional acidity function method are discussed. The relevant background in the preparation and use of phosphonic acid containing compounds as intermediates for reactive dyestuffs is briefly discussed and the dyeing of cotton fabrics is outlined.
| Identifer | oai:union.ndltd.org:bl.uk/oai:ethos.bl.uk:637744 |
| Date | January 1986 |
| Creators | Jurczyk, S. |
| Publisher | Swansea University |
| Source Sets | Ethos UK |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
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