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.

Comments

Includes bibliograhpical references.||Includes illustrations.

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

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