Please use this identifier to cite or link to this item: http://hdl.handle.net/1893/31102
Appears in Collections:eTheses from Faculty of Natural Sciences legacy departments
Title: Kinetic and product analytical study of the effect of substituents upon the solvolysis of benzyl azoxytosylate in aqueous trifluoroethanol
Author(s): Gordon, Isobel M
Issue Date: 1989
Publisher: University of Stirling
Abstract: Six variously substituted benzyl azoxytosylates, ((1) a: X=4-OCH3, 4-CH3, S-CH3, H, 4-CI, S-CI; Y=4-CH3) three 4-methylbenzyl 4-substituted-azoxyarenesulphonates, ((1) b: X=4-CH3; Y=CW, Br, OCH3), three 3-chlorobenzyl 4-substituted-azoxyarenesulphonates, ((1) c: X=3-CI; Y=CW. Br, OCH3) and three 3-chlorobenzyl 4-substituted-arenesulphonates, ((2): X=3-C1; Z=CW, Br, OCH3) have been prepared, and the rates and activation parameters of their solvolysis in 1:1 v/v aqueous 2,2,2-trifluoroethanol studied. For each series of compounds k28°c ¬has been correlated with v or v¬- in a Hammett-type study and the following p-values were obtained1- (1)a: p(r+) = -S.27, r > 0.999; (1)b: p(σ) = +1.37, r > 0.999. Using these p-values, it has been established, that, in the transition state of the solvolysis of (1), the cleavage of bonds (a) and (b) is concerted. In addition, from the relative magnitude of the p-values, the position of the transition state on the reaction map has been deduced. The unusual correlation of compounds (1)c with v- (p is positive) is discussed in terms of resonance stabalisation of the ground state by electron withdrawing substituents. Product analyses (some of a preliminary nature) have been carried out of the solvolysis of (1)a: X= 4-CH3, 4-OCH3, 3-CI and the arenesulphonates, (2).
Type: Thesis or Dissertation
URI: http://hdl.handle.net/1893/31102

Files in This Item:
File Description SizeFormat 
Gordon-Thesis.pdf5.17 MBAdobe PDFView/Open



This item is protected by original copyright



Items in the Repository are protected by copyright, with all rights reserved, unless otherwise indicated.

If you believe that any material held in STORRE infringes copyright, please contact library@stir.ac.uk providing details and we will remove the Work from public display in STORRE and investigate your claim.