Nitration of 1‐dodecene with nitric acid

Abstract A refluxing, heterogeneous mixture of l‐dodecene with aqueous 30% nitric acid leads to a mixture of closely related nitroproducts in greater than 90 % yield within 3 h. Similarly various types of readily available olefins easily undergo nitration with nitric acid. The nitration of l‐dodecene with nitric acid is initiated by nitrous acid, exhibits free‐radical character and is believed to proceed through the agency of nitrogen dioxide although the manner of its propagation is not fully clear. However, a rate‐determining oxidation step apparently determines both the variation of nitration time with change in olefin structure and also the temperature dependence of the rate of nitroproduct formation. Emulsifying agents increase the nitration rate and the slow addition of sufficient nitrous acid obviates the reaction's temperature dependence.