Citation
Lemaire, Henry (1950) Addition to the Carbon-Carbon Triple Bond. The Reaction of Acetic Acid with 3-Hexyne. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/5g6h-b137. https://resolver.caltech.edu/CaltechTHESIS:10312023-185511760
Abstract
The mechanism of the mercury-catalyzed addition to the carbon-carbon triple bond has been investigated. Acetic acid was used as the solvent and one reactant. The other reactant was 3-hexyne. The course of the reaction was followed by bromine titration and by a special indicator method. The addition was found to take place in two discrete steps, forming 3-acetoxyhexene-3 and 3-hexanone.
The rate of the initial reaction was determined for a range of initial concentrations of hexyne and the catalysts. When mercuric acetate and perchloric acid were used as the catalysts , the initial rates were found to be interpretable on the assumption that the reactive species was a 1 to 1 to 1 complex formed by the 3-hexyne, the mercuric acetate, and the perchloric acid. By means of indicator studies the existence of the 1 to 1 to 1 complex (probably a hexyne-mercuric monoacetate cation) was proved and its equilibrium constant measured.
The indicator studies were extended to the measurement of the basicities of weak bases in acetic acid. A simple relationship was found between the observed ionization constant and the thermodynamic activity constant. New values were found for the basic strengths of dioxane, acetonitrile, p-toluene-sulfonamide, water, acetanilide, acetamide, and urea.
Item Type: | Thesis (Dissertation (Ph.D.)) |
---|---|
Subject Keywords: | (Chemistry and Physics) |
Degree Grantor: | California Institute of Technology |
Division: | Chemistry and Chemical Engineering |
Major Option: | Chemistry |
Minor Option: | Physics |
Thesis Availability: | Public (worldwide access) |
Research Advisor(s): |
|
Thesis Committee: |
|
Defense Date: | 1950 |
Record Number: | CaltechTHESIS:10312023-185511760 |
Persistent URL: | https://resolver.caltech.edu/CaltechTHESIS:10312023-185511760 |
DOI: | 10.7907/5g6h-b137 |
Default Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. |
ID Code: | 16224 |
Collection: | CaltechTHESIS |
Deposited By: | Kathy Johnson |
Deposited On: | 31 Oct 2023 19:04 |
Last Modified: | 31 Oct 2023 19:18 |
Thesis Files
PDF
- Final Version
See Usage Policy. 51MB |
Repository Staff Only: item control page