<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 / Thesis / Master of Science (MSc)
| Identifer | oai:union.ndltd.org:mcmaster.ca/oai:macsphere.mcmaster.ca:11375/19245 |
| Date | January 1986 |
| Creators | McCallion, J. |
| Contributors | Warkentin, John, Chemistry |
| Source Sets | McMaster University |
| Language | English |
| Detected Language | English |
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