Condensation of terephthalaldehyde and hydroxyacetophenones

Author

Ernest John Bonelli, University of the Pacific

Date of Award

1959

Document Type

Thesis

Degree Name

Master of Science (M.S.)

Department

Chemistry

First Advisor

Emerson G. Cobb

Abstract

Organic pigments were the source of coloring matters used by man until comparatively recent times. It is to be presumed that the first steps in the use of these pigments no dyes resulted from the accidental staining of the skin or fabric by a vegetable material. Prehistoric man, in order to decorate his implements or his person, or even to make records of his mode of life, used the materials with which he came in daily contact. Coloring materials included earth and vegetable substances found in flowers, seeds, berries, nuts, bark, wood, and roots, and less readily available coloring materials such as those of the heavy metals and those of animal origin.

In addition to his knowledge of dyestuffs prehistoric man also developed a knowledge of tanning. He found that some of the vegetation that provided him with coloring matter would also preserve the skins he removed from the animals he killed as food and in doing so would render them suitable for clothing.

Shortly after the preparation of the first synthetic dyestuff, the investigation of the natural yellow coloring matters was undertaken by Herzig. Herzig studied quercetin, derived from quercitron bark, and fisetin, which is present in young fuatic. About the same period, von Kostanecki submitted to examination chrysin, a coloring matter which had been isolated from the bud of the common popular. From the properties of this substance and the fact that when hydrolyzed it yields acetophenone and phloroglucinol, von Kostanecki represented it as a dihydroxy phenyl benzo-α-pyrone (I). von Kostanecki designated the mother substance of chrysin as being flavone (II), whereas the mother substance of fisetin (III) was flavonol (IV).

The preparation of terephthalates was investigated in this work. The two methods considered were: (1) The condensation of terephthalaldehyde with the benzoates of o-hydroxyacetophenone, o,p-hydroxyacetophenone and o,m,p-trihydroxyacetophenone respectively in dry ethyl acetate using dry hydrogen chloride as the condensing agent, with subsequent debenzylation with 10 percent sodium hydroxide in an atmosphere of nitrogen. (2) The condensation of terephthalaldehyde with o-hydroxyacetophenone and o,p-hydroxyacetophenone using sodium hydroxide as the condensing agent.

The dying properties of the compounds were investigated by precipitating the hydroxides of chromium, aluminum and iron salts as modante on woolen patches. The dyes of the latter two mordante were water fast, whereas those of the chromium mordent were not.

Pages

42

Recommended Citation

Bonelli, Ernest John. (1959). Condensation of terephthalaldehyde and hydroxyacetophenones. University of the Pacific, Thesis. https://scholarlycommons.pacific.edu/uop_etds/1416