Physical Sciences and Mathematics Commons^™

Metal Salt Catalyzed Carbenoids Ii, Robert Stephen Mcdaniel Jr.

Doctoral Dissertations

"The interaction of diazomalonic esters with olefins in the presence of homogeneous Cu(II) catalyst species has been examined relating to olefin structure effects and catalyst structure effects using partial rate data as a method of determining the mechanistic aspects of the various reactions.

It has been possible to examine the mechanistic details of cyclopropanation, C-H insertion, and both "dimer" forming reactions.

Cyclopropanation proceeds via a transition state including olefin, copper (II), ligands, and carbene C-H insertion results from hydrogen abstraction prior to collapse of the transition state. "Dimer" is formed by the attack of diazo compound on the carbenoid carbon, …

Kinetic And Thermodynamic Acidities Of Selected Weakly Acidic Hydrocarbons, Darrell R. Strait

Doctoral Dissertations

"The kinetic and thermodynamic acidities in methanol for bromoform and phenylacetylene have been determined at various temperatures. The thermodynamic acidities of phenylacetylene were obtained through a quench method which involved tritium tagging of the phenylacetylene anions present at equilibrium. With the use of this method, a pK_a of 18.34 for phenylacetylene at 0ºC was obtained. Through the use of these acidities, it was shown that the kinetics for these proton exchange processes are not diffusion controlled.

Isotope effects ( k_H/ k_D) were obtained for chloroform, bromoform and phenylacetylene at three temperatures (0ºC, -10ºC and -20ºC). …

The Chemical And Electrochemical Oxidative Decarboxylation Of Methyliminodiacetic Acid In Acid Media, Rita Kathleen Hessley

Doctoral Dissertations

"Methyliminodiacetic acid (MIDA) is oxidized with cerium. (IV) in both perchloric and sulfuric acids to give sarcosine, formaldehyde, and carbon dioxide"--Abstract, page 2.

A Study Of The Kinetic And Thermodynamic Properties Of Carbon Acids In Methanol, Dennis L. Filger

Doctoral Dissertations

The thermodynamic acidity (pK_a) of iodoform in methanol was determined at 25°C and 35°C; the values are 18.74 and 18.05, respectively . These acidity constants were determined by a modification of the equilibrium quenching technique which involves the conversion of the conjugate base of iodoform, present at equilibrium, to the radioactively labelled acid.

The rate constants for the methoxide-catalyzed hydrogentritium exchange of chloroform, iodoform, 9-phenylfluorene and indene were determined in methanol at various temperatures. The second-order rate constants obtained from these studies were shown to be the rate constants for removal of a triton. The activation parameters (ΔH …

Base-Induced Reactions Of P-Nitrobenzyl Compounds, Paul Henry Ruehle

Doctoral Dissertations

"The base-induced reactions of several p-nitrobenzyl compounds were studied. The products varied with changes in the leaving groups. With relatively poor leaving groups (Cl, S⁺(Me)₂), p,p'- dinitrostilbene was produced in good yield. The products of the reaction of p-nitrobenzyl chloride and hydroxide ion in 50% aqueous dioxane were 52.0% p,p'-dinitrostilbene, 43.9% cis- and trans-p,p'-dinitrostilbene oxides, 3.2% p-nitrobenzyl alcohol, and traces of other compounds. With dissolved oxygen, no stilbene was produced; the main product was 88% cis- and trans-p,p'-dinitrostilbene oxides. The addition of small amounts of di-t-butyl nitroxide caused a decrease in both the rate of the reaction and the amount …