A. Orcinol dimethyl ether. A 1-l., three-necked flask fitted with a mechanical stirrer, a condenser, and a 100-ml. dropping funnel is charged with 124 g. (0.984 mole) of anhydrous potassium carbonate, 410 ml. of acetone (Note 1), and 42.6 g. (0.344 mole) of orcinol monohydrate (Note 2). The stirrer is started, and 94.5 g. (70.9 ml., 0.750 mole) of dimethyl sulfate is added from the dropping funnel to the pink mixture over a period of 2 minutes. The mixture warms appreciably and begins to reflux after an additional 5 minutes. When the spontaneous boiling has subsided (15–20 minutes after addition of the dimethyl sulfate), the stirred mixture is heated gently under reflux for 4 hours longer. The condenser is then arranged for distillation and 200 ml. of acetone is distilled. A 50-ml. portion of concentrated aqueous ammonia is added to the reaction mixture; stirring and heating are continued for 10 minutes. The mixture is diluted with water to a total volume of approximately 750 ml., the layers are separated, and the organic layer is combined with two 150-ml. ethereal extracts of the aqueous layer. The organic phase is washed with 50 ml. of water, twice with 50-ml. portions of 3 N sodium hydroxide solution (Note 3), once with 50 ml. of saturated aqueous sodium chloride, and dried over magnesium sulfate. After evaporation of the ether at atmospheric pressure, the residual liquid is distilled under reduced pressure, yielding 42.9–43.7 g. (94–96%) of orcinol dimethyl ether, b.p. 133–135° (40 mm.) (Note 4) and (Note 5).

B. Orcinol monomethyl ether. A 1-l., three-necked flask equipped with a magnetic stirrer, a condenser, a dropping funnel, and a nitrogen inlet is charged with 250 ml. of dry N,N-dimethylformamide (Note 6) and 22 g. (0.55 mole) of sodium hydride (60% oil dispersion). The suspension is stirred under an atmosphere of dry nitrogen and cooled with an ice bath while a solution of 31 g. (37 ml., 0.50 mole) of ethanethiol (Note 7) in 150 ml. of dry N,N-dimethylformamide (Note 6) is added slowly from the dropping funnel over a period of 20 minutes. The ice bath is removed and stirring is continued for an additional 10 minutes. A solution of 38.0 g. (36.5 ml., 0.250 mole) of orcinol dimethyl ether in 100 ml. of dry N,N-dimethylformamide (Note 6) is added in one lot, and the mixture is refluxed under an atmosphere of dry nitrogen for 3 hours (Note 8) and (Note 9). The mixture is cooled, poured into 1.8 l. of cold water, and extracted with two 250-ml. portions of petroleum ether (b.p. 50–70°), which are discarded. The aqueous layer is acidified with 330 ml. of ice-cold 4 N hydrochloric acid and extracted with three 250-ml. portions of ether. The combined ethereal extracts are washed with 100 ml. of saturated aqueous sodium chloride and dried over magnesium sulfate. After the ether is distilled at atmospheric pressure, the residual liquid is distilled under reduced pressure, yielding 28–30.5 g. (81–88%) of orcinol monomethyl ether, b.p. 89–90° (0.2 mm.) or 156–158° (25 mm.) (Note 10) and (Note 11)