- Collection:
- Atlanta University and Clark Atlanta University Theses and Dissertations
- Title:
- Studies on the reduction of propargylic alcohols with trimethylsilylchloride, potassium iodide, and acetonitrile, 2004
- Creator:
- Haas, Julia
- Date of Original:
- 2004-12-01
- Subject:
- Degrees, Academic
Dissertations, Academic - Location:
- United States, Georgia, Fulton County, Atlanta, 33.749, -84.38798
- Medium:
- theses
- Type:
- Text
- Format:
- application/pdf
- Description:
- Silylated propargylic alcohols were prepared by the addition of trimethylsilylacetylene to the corresponding ketones. Non-silylated alcohols were obtained from the silylated species by deprotection of the silyl-group with potassium carbonate in methanol. The reduction of these alcohols with trimethylsilylchoride/potassium iodide in acetonitrile was investigated. The reduction of silylated diaryl propargylic alcohols gave allylsilanes as the major product when six equivalents of trimethylsilylchoride/potassium iodide in acetonitrile/hexane and long reaction times were employed. The propargylic alcohols derived from fluorenone; benzophenone, o-dichloro-benzophenone and acetophenone could be converted to the corresponding allylsilanes in good yields (54-90%). At shorter reaction times, allenes were isolated. For propargylic alcohols derived from aromatic aldehydes, allenes were the major products with yields ranging from 43 to 78 percent.The behavior of non-silylated propargylic alcohols was also investigated. Reduced dimerization products and alkanes were obtained. Several mechanistic studies were conducted to determine the source of hydrogen for the reduction. For these reductions, it was determined that acetonitrile, hexane and water were not the source of hydrogen atoms. Pyridine proved to inhbit the reaction.
- External Identifiers:
- Metadata URL:
- http://hdl.handle.net/20.500.12322/cau.td:2004_haas_julia.pdf
- Rights Holder:
- Clark Atlanta University
- Holding Institution:
- Atlanta University Center Robert W. Woodruff Library
- Rights:
-
