Thirteen hundred milliliters of 1,2-dimethoxyethane (glyme) is distilled from lithium aluminum hydride (Caution! Under no circumstances should distillation be carried to dryness since explosive decomposition of the residual hydride may occur.) (Note 2) directly into a 2-l., nitrogen-flushed, three-necked, Morton flask equipped with a nitrogen inlet, an outlet, and a high-speed stirrer with a stainless steel propeller-type blade. The flask is charged with 89.7 g. (0.87 mole) of t-nitrobutane (Note 3) and 19.9 g. (0.87 g. atom) of sodium cut into pea-sized pieces (Note 4). The stirrer is started and initially operated at a speed just adequate to draw some of the sodium through the blade. The onset of reaction is signaled when the solution is pale lavender and the sodium surface is clearly etched and colored bright gold (Note 5). The temperature of the reaction mixture is maintained at 25–30° (Note 6) by directing an air blast at the sides of the flask and by controlling the rate at which sodium is drawn through the blades of the stirrer. As the reaction progresses, colorless solid is formed, and at the end of the reaction (ca. 24 hours) the reaction mixture consists of solid and a colorless glyme solution. Most of the glyme is removed by evaporation under reduced pressure at room temperature with a water bath at 20–25° to leave a thick, colorless slurry. To the slurry under nitrogen (Note 7) is added 270 ml. of water, and the reddish brown organic layer is separated. The aqueous layer (Note 8) is extracted with several portions of pentane until the extract is colorless. The organic layer and pentane extracts are combined, cooled to 0°, and washed rapidly and thoroughly with two 70-ml. portions of ice-cold 0.25N hydrochloric acid to remove hydroxylamine impurities (Note 9). The pentane solution of the product is washed immediately with 70 ml. of cold water followed by 70 ml. of cold, aqueous 0.2N sodium hydroxide. The combined, cold, aqueous acidic washings are extracted with small portions of pentane until colorless. This pentane extract is used to extract the aqueous sodium hydroxide layer and is then washed with water and combined with the initial pentane extract.

The pentane solution is dried over anhydrous magnesium sulfate and fractionated with an efficient spinning-band column (Note 10). After foreruns of pentane and glyme containing t-nitrosobutane are removed (Note 11), 26–27 g. (42–43%) of red di-t-butyl nitroxide, b.p. 59–60° (11 mm.), is obtained.