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Kinetic and N.M.R. Studies of Carbon Acids in Basic Media.

Walkin, Kevin T. (1979) Kinetic and N.M.R. Studies of Carbon Acids in Basic Media. Doctoral thesis, University of Surrey (United Kingdom)..

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The thesis is divided into four chapters. Chapter one is concerned with the detritiation from labelled compounds containing more than one exchangeable site. The compounds chosen for study were m-dinitrobenzene and a variety of amino acids. The amino acids were labelled using enzyme catalysed exchange and the various kinetics of enzyme catalysed detritiation were studied. The computer programme used was successful in evaluating the kinetics of detritiation of m-dinitrobenzene and L-alanine labelled in two positions and a mixture of aspartic and glutamic acids each labelled in only one position. Chapter two is concerned with a variety of methods that were used to label some polynitrobenzenes and polynitro naphthalenes. The labelling patterns were determined using tritium nmr spectroscopy. A variety of different labelling patterns were obtained and some of the reasons for this are discussed. The preparation of the "Meisenheimer" complex of s-trinitrobenzene and the tritium nmr spectrum of this complex is described. Chapter three is concerned with kinetic methods of observing ion pairing in solution. The reactions studied were simple detritiation or cleavage reactions in isopropanol, as catalysed by sodium and potassium isopropoxide. Some attempts were made to quantify the free ion and ion pair rate constants in these media. Difficulties were encountered when sodium and potassium tetraphenylboron were used as salts in these media and some experiments are described which highlight the problems involved and which also suggest methods of circumventing them. Finally, in chapter four, a study is described of experiments carried out on a variety of different detritiation reactions catalysed by sodium hydroxide in water and sodium alkoxides in methanol, ethanol, isopropanol and t-butanol. The carbon acids studied are chloroform, s-trinitrobenzene, acetophenone, p-dimethylaminoaceto-phenone, dimethylsulphone and phenylacetylene. The cleavage reaction of p-nitrobenzyltrimethylsilane was also studied in these media. Correlations with dielectric constant of the medium and with H are described.

Item Type: Thesis (Doctoral)
Divisions : Theses
Authors :
Walkin, Kevin T.
Date : 1979
Contributors :
Additional Information : Thesis (Ph.D.)--University of Surrey (United Kingdom), 1979.
Depositing User : EPrints Services
Date Deposited : 22 Jun 2018 15:17
Last Modified : 06 Nov 2018 16:54

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