A. Reduction and hydrolysis. A solution of 129 g. (0.75 mole) of β-naphthyl ethyl ether in 1.5 l. of 95% ethanol is prepared in a 5-l. three-necked flask fitted with a mechanical stirrer, a bulb condenser topped by a Friedrichs condenser, and a Y-tube to allow for the introduction of nitrogen and sodium. The apparatus is flushed thoroughly with nitrogen, the nitrogen flow is reduced, and 225 g. (9.8 g. atoms) of sodium is added in small portions (Note 1), with efficient stirring, at a rate sufficient to maintain vigorous boiling. The hydrogen liberated passes through the condensers and a delivery tube into a hood or directly out a window. When approximately two-thirds of the sodium has been introduced, an additional 375 ml. of 95% ethanol is added to reduce the viscosity of the reaction mixture. Approximately 1.5 hours is required for the addition of the sodium. Near the end of this period, the rate of the reaction decreases and heat is supplied by means of an electric heating mantle to maintain the reflux temperature (Note 2).

After all the sodium has dissolved, the hydrogen is thoroughly swept from the system with nitrogen and the heating is discontinued. The Y-tube is replaced by a separatory funnel, and 750 ml. of water is added cautiously (Note 3), with stirring, followed by 1.5 l. of concentrated hydrochloric acid (Note 3). The acidic mixture containing precipitated sodium chloride is heated, with stirring, at the reflux temperature for 30 minutes, and then allowed to cool.

The mixture is extracted with ten 175-ml. portions of benzene or 1:1 benzene-ether mixture (Note 4). The combined extract is washed with 75-ml. portions of water until the washings are neutral to litmus. The organic solvent is removed by distillation on a steam bath. The crude oily residue is converted directly (Note 5) to the β-tetralone bisulfite addition product.

B. Bisulfite addition product of β-tetralone. To a solution of 325 g. (3.12 moles) of sodium bisulfite (commercial purified grade) in 565 ml. of water is added 175 ml. of 95% ethanol. The mixture is allowed to stand overnight, and the precipitated sodium bisulfite is removed by filtration. The filtrate is added to the crude β-tetralone, and the mixture is shaken vigorously. Within a few minutes the addition product separates as a voluminous precipitate. The mixture is kept cold for several hours, shaken periodically, and then filtered with the aid of suction. The precipitate is washed well, first with 125 ml. of 95% ethanol, then four times with 125-ml. portions of ether (Note 6). The colorless addition product is air-dried (Note 5) and is stored in air-tight containers. The yield is 113–131 g. (60–70% based on β-naphthyl ethyl ether) (Note 7).

C. Regeneration of β-tetralone. Fifty grams (0.20 mole) of β-tetralone bisulfite addition product is suspended in 250 ml. of water, and 75 g. (0.6 mole) of sodium carbonate monohydrate is added. At this point the pH of the solution is approximately 10. The mixture is extracted with five 100-ml. portions of ether (Note 8). The combined extract is washed with 100 ml. of 10% hydrochloric acid, then with 100-ml. portions of water until the washings are neutral to litmus, and is dried over anhydrous magnesium sulfate. The ether is removed by distillation, and the residue is distilled from a Claisen flask under reduced pressure, preferably in a nitrogen atmosphere. The pure β-tetralone is obtained as a colorless distillate; b.p. 70–71°/0.25 mm. (92–94°/1.8 mm., 114–116°/4.5 mm.); n_D20 1.5594. The yield is 17–21 g. (40–50% based on β-naphthyl ethyl ether).