Experimental from JACS 75, 3004 (1953)
2,5-Dimethoxyphenethyl alcohol
n-Butyllithium was prepared from lithium (28g) and n-butyl chloride (180g) in dry ether (350 ml.). A solution of hydroquinone dimethyl ether (205g) in dry ether (776mL) was added in one portion and the solution allowed to stand for 15 hours. The reaction mixture was maintained at 0°C while ethylene oxide (130g) was passed in as a gas during 3 hours. After standing overnight the reaction mixture was poured into ice-water (2 liters). The organic layer was separated, dried and fractionated. There was obtained 182g (68%) of product, bp 130-142°C/0.7mmHg, n25D 1.5402.
This alcohol formed a p-nitrobenzoate which melted at 73-74°C. From the distillation residue (20g) 6g of a crystalline by-product, mp 134-135°C, was isolated.
2,5-Dimethoxyphenethyl Bromide
A solution of 2,5-Dimethoxyphenethyl alcohol (66g) in benzene (65 ml) was stirred and cooled in an ice-bath while phosphorus tribromide (30g) in benzene (50 ml) was added dropwise. The solution was kept at 0-5°C for two hours and then at 60°C for four hours. Ice-water was added to the cool reaction mixture and the organic layer was separated. The benzene solution of crude bromide was washed with ice-cold 5% sodium hydroxide solution, water and dilute hydrochloric acid. Acidification of the sodium hydroxide extract yielded about 20g of an oil containing phenolic by-products. The benzene solution was concentrated and the residual crude bromide distilled rather quickly at a low pressure and temperature. There was obtained 48g (54%) of 2,5-Dimethoxyphenethyl Bromide, bp 97-110°C/0.25mmHg, n24D 1.5542. There is decomposition of this bromide with distillation and in three separate attempts an analytically pure sample could not be prepared, some loss of hydrogen bromide took place even with evaporative distillation.