Synthetic and Mechanistic Investigations of the Chemistry of a α-Substituted Diazenes

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