Publication Date
1981
Document Type
Dissertation/Thesis
First Advisor
Spangler, Charles W.
Degree Name
M.S. (Master of Science)
Legacy Department
Department of Chemistry
LCSH
Organonitrogen compounds; Diels-Alder reaction; Halogenation
Abstract
3-Acetoxy-l,3,5-hexatriene and 3-ethoxy-l,3,5-hexatriene were prepared by the elimination of HBr from an appropriately substituted dienyl bromide using DBU as the dehydrohalogenating reagent. 3-Ethoxy- 1.3.5- hexatriene was also prepared by the pyrolytic elimination of HOAc from the appropriately substituted dienol. 1-Trimethylsiloxy- 1.3.5- hexatriene was prepared by the addition of chlorotrimethylsilane to 2,4-hexadienal catalyzed by triethylamine and zinc chloride. The route used to prepare 3-acetoxy- and 3-ethoxy-l,3,5-hexatriene involved the synthesis of 3-acetoxy-l,5-hexadien-4-ol and 3-ethoxy- 1.5- hexadien-4-ol. These alcohols were converted to the corresponding allylic bromides and treated with l,8-diazabicyclo[5.4.0]undec-7-ene to effect dehydrohalogenation. 3-Ethoxy-l,5-hexadien-4-ol was also converted to the corresponding acetate, which was then thermolyzed to yield impure 3-ethoxy-1,3,5-hexatriene. The heteroatom substituted-l,3,5-hexatrienes were reacted with acrolein, methacrolein, and methyl vinyl ketone to determine their usefulness as Diels Alder reagents. NMR analysis of the products resulting from the reaction of 3-acetoxy-l,3,5-hexatriene with the dienophiles was accomplished. The Diels Alder products from 3-ethoxy- 1.3.5- hexatriene and 1-trimethylsiloxy-l,3,5-hexatriene were not isolated due to the sensitivity of the ethoxy and trimethylsiloxy functions to preparative glpc. For these adducts the unreacted dienophiles were removed by high vacuum evaporation and the presence of Diels Alder products were confirmed by the nmr signals of the dienophile substituents.
Recommended Citation
Zentner, Brian A., "Synthesis of 3-acetoxy and 3-ethoxy-1,3,5-hexatrienes and a preliminary evaluation of their effectivness as Diels-Alder reagents" (1981). Graduate Research Theses & Dissertations. 5186.
https://huskiecommons.lib.niu.edu/allgraduate-thesesdissertations/5186
Extent
vi, 62 pages
Language
eng
Publisher
Northern Illinois University
Rights Statement
In Copyright
Rights Statement 2
NIU theses are protected by copyright. They may be viewed from Huskie Commons for any purpose, but reproduction or distribution in any format is prohibited without the written permission of the authors.
Media Type
Text
Comments
Includes bibliograhpical references.||Includes illustrations.