Methylenecyclohexane and N,N-Dimethylhydroxylamine hydrochloride could be produced through the following synthetic routes.

In a carefully cleaned 500-ml. Erlenmeyer flask, covered with a watch glass, are placed 49.4 g. (0.35 mole) of N,N-dimethylcyclohexylmethylamine, 39.5 g. (0.35 mole) of 30% hydrogen peroxide, and 45 ml. of methanol. The homogeneous solution is allowed to stand at room temperature for 36 hours. After 2 and 5 hours hydrogen peroxide (39.5-g. portions each time) is added. The excess hydrogen peroxide is destroyed by stirring the mixture with a small amount of platinum black until the evolution of oxygen ceases. The solution is filtered into a 500-ml. round-bottomed flask and concentrated at a bath temperature of 50–60°, a aspirator being used initially and an oil pump finally, until the amine oxide hydrate solidifies. A -covered stirring bar is introduced into the flask, which is then connected by a 20-cm. column to a trap (reversed to avoid plugging) cooled in Dry Ice-acetone. The flask is heated in an oil bath to 90–100°, and the apparatus is evacuated to a pressure of ca. 10 mm. with stirring of the liquefied amine oxide hydrate. When the content of the flask resolidifies, the temperature of the oil bath is raised to 160°. The amine oxide decomposes completely within about 2 hours at this temperature. Water (100 ml.) is added to the contents of the trap. The olefin layer is removed with a pipette and washed with two 5-ml. portions of water, two 5-ml. portions of ice-cold 10% hydrochloric acid, and one 5-ml. portion of 5% sodium bicarbonate solution. The olefin is cooled in a Dry Ice-acetone bath and filtered through glass wool. Distillation over a small piece of sodium through a semimicro column2 yields 26.6–29.6 g. (79–88%) of methylenecyclohexane, b.p. 100–102°, n²⁵D 1.4474.

The aqueous layer is combined with the two neutral aqueous extracts and acidified by addition of 45 ml. of concentrated hydrochloric acid. The solution is concentrated under reduced pressure at 60–70° until no more distillate comes over. The residue, which solidifies on cooling, is dried in a vacuum desiccator over potassium hydroxide pellets to yield 30.7–32.7 g. (90–96%) of crude N,N-dimethylhydroxylamine hydrochloride, m.p. 103–106° (sealed tube). Crystallization from 40 ml. of isopropyl alcohol gives 26.6–30.7 g. (78–90%) of the pure hydrochloride, m.p. 106–108° (sealed tube).