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Addition to the Carbon-Carbon Triple Bond. The Reaction of Acetic Acid with 3-Hexyne

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):
  • Lucas, Howard J.
Thesis Committee:
  • Unknown, Unknown
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

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