Nucleophilic Reactions Of Sulfonyl And Carbonyl Compounds

This thesis contains topics in organic sulfur chemistry and general physical organic chemistry. In the first chapter a pH rate profile (log {dollar}k\sb{lcub}\rm obs{rcub}{dollar} vs pH) was determined for the hydrolysis of ethylene sulfone (1) over the pH range from 4 to 11.5 at 75{dollar}\sp\circ{dollar}C. The rate constant {dollar}k\sb{lcub}\rm obs{rcub}{dollar} was found to be of the form {dollar}k\sb{lcub}\rm obs{rcub}{dollar} = {dollar}k\sb{lcub}\rm w{rcub}{dollar} + {dollar}k\sb{lcub}\rm OH{rcub}{dollar} (OH{dollar}\sp-{dollar}) where {dollar}k\sb{lcub}\rm w{rcub}{dollar} = (8.71 {dollar}\pm{dollar} 1.38) {dollar}\times{dollar} 10{dollar}\sp{lcub}-5{rcub}{dollar} s{dollar}\sp{lcub}-1{rcub}{dollar} and {dollar}k\sb{lcub}\rm OH{rcub}{dollar} = (2.98 {dollar}\pm{dollar} 0.89) {dollar}\times{dollar} 10{dollar}\sp{lcub}-2{rcub}{dollar} M{dollar}\sp{lcub}-1{rcub}{dollar}s{dollar}\sp{lcub}-1{rcub}{dollar}. In the pH region that corresponds to the uncatalyed hydrolysis ({dollar}k\sb{lcub}\rm w{rcub}{dollar}, pH 4 to 9) the product of the reaction is 2-hydroxyethanesulfinate (9) from the attack of water at the carbon of 1. The major product of the reaction at pH 11.5 is ethanesulfonate (3) with small quantities of 9 also being produced.;The second chapter is devoted to stereoelectronic effects in sulfonamides and their effects on the p{dollar}K\sb{lcub}\rm a{rcub}{dollar}\u27s of constrained sulfonamides relative to the p{dollar}K\sb{lcub}\rm a{rcub}{dollar}\u27s of simple dialkyl derivatives. The synthetic routes to the simple, monocyclic and bicyclic sulfonamides are described. p{dollar}K\sb{lcub}\rm a{rcub}{dollar}\u27s were determined by the method of Laughlin and the excess acidity method of Cod and Yates and the two methods were found to give the same results.;Chapter 3 is concerned with the application of the stereoelectronic effects which are present in sulfonamides to chemical reactivity. Rate constants for the hydrochlorinolysis of constrained sulfonamides were measured at a number of elevated temperatures. The reported mechanism for the acid-promoted cleavage reaction of N-methyl {dollar}\gamma{dollar}-sultam (6) in aqueous hydrochloric acid allows separation of the observed rate constants into terms which are derived principally from steric effects ({dollar}k\sb2{dollar}) and from protonation effects.;In chapter 4 the pH optimization concept has been extended to include the reactions of simple amines (aniline (1) and benzylamine (4)) with ethyl chloroformate (12) and to the selective acetylation of a p-aminobenzylamine (15) with acetic anhydride (17). A pH rate profile was determined for the hydrolysis of ethyl chloroformate (12). The observed rate constant for the hydrolysis of 12 in 0.05 M NaCl at 25{dollar}\sp\circ{dollar}C was in agreement with the equation {dollar}k\sb{lcub}\rm obs{rcub}{dollar} = {dollar}k\sb{lcub}\rm w{rcub}{dollar} + {dollar}k\sb{lcub}\rm OH{rcub}{dollar} (OH{dollar}\sp-{dollar}) where {dollar}k\sb{lcub}\rm w{rcub}{dollar} = 4.85 {dollar}\times{dollar} 10{dollar}\sp{lcub}-4{rcub}{dollar} s{dollar}\sp{lcub}-1{rcub}{dollar} and {dollar}k\sb{lcub}\rm OH{rcub}{dollar} = 40.6 M{dollar}\sp{lcub}-1{rcub}{dollar}s{dollar}\sp{lcub}-1{rcub}{dollar}. (Abstract shortened by UMI.