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Title: | Synthetic and Mechanistic Investigations of the Chemistry of a α-Substituted Diazenes |
Authors: | McCallion, J. |
Advisor: | Warkentin, John |
Department: | Chemistry |
Keywords: | α-Substituted Diazene;mechanistic investigation;chemistry;hydroperoxydiazenes |
Publication Date: | 1986 |
Abstract: | <p> It had been proposed that α-hydroperoxydiazenes decompose by the radical chain abstraction of the hydroxy group. This suggested that these compounds could be used as hydroxyalkylating agents for unsaturated systems. </p> <p> Compounds 15 and 23 were prepared by the autoxidation of the corresponding hydrazone. α-Hydroperoxydiazenes 15 and 23 were used to hydroxyalkylate ethyl vinyl ether and 2-methoxypropene in yields of 62-65%. Mechanisms of the addition reaction are discussed. </p> <p> In an attempt to alkylate a hetero atom system, ·compound 15 was thermolyzed with compound 25. The alkylation product was not obtained. </p> <P> Compound 15 was converted to α-hydroxydiazene 34 by the action of Φ3P. α-Hydroxydiazine have been used synthetically in the hydroalkylation of alkenes. The rate constant of hydrogen abstraction was determined to be in the range of 1.5 x 10^5 M^-ls^-l to 1.5 x 10^7 M^-ls^-l by the use of a radical clock reaction. An upper limit on the rate of rearrangement of the 2-cyanopropyl radical was found to be 3.65 x 10^3 s^-1 . </p> A new compound (23) was prepared |
URI: | http://hdl.handle.net/11375/19245 |
Appears in Collections: | Open Access Dissertations and Theses |
Files in This Item:
File | Description | Size | Format | |
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McCallion_J_D_1986_Masters.pdf | 13.68 MB | Adobe PDF | View/Open |
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