Ethyl Bromide → 2-Pent-2-ynyloxy-tetrahydro-pyran

Participants

Reaction Steps

0.89 g (127 mmol) of granulated lithium were added within 5 minutes to 100 ml (4 mol) of liquid ammonia at −38° C. The mixture was stirred until no more lithium floated (after approximately 10 minutes). A dark blue solution of lithium in liquid ammonia was obtained. Isoprene (5.94 g, 86 mmol) was added portion wise within 20 minutes. The reaction mixture was held at −38° C. for about 15 minutes. The end of the formation of Li-amide could be recognized by the de-coloration of the reaction mixture. 11.33 g (70 mmol) of 2-prop-2-ynyloxy-tetrahydropyran were added via a dropping funnel to the reaction mixture at −38° C. within 20 minutes. The reaction mixture was held at −38° C. for about 1 hour. Ethyl bromide 14.0 g (126 mmol) was added via a dropping funnel to the reaction mixture within 20 minutes. The reaction mixture was subsequently stirred for 1 hour. 100 ml n-hexane was added to the reaction mixture and the liquid ammonia was evaporated under normal pressure within 1.5 hours. 50 ml of water was added to the reaction mixture at 22° C., and the mixture was stirred until all salt was dissolved. The water layer was extracted twice with 50 ml n-hexane. The organic layer was dried over 5 g of anhydrous sodium sulfate. The solution was concentrated under reduced pressure (40° C., 60 mbar) and the crude product was analyzed by GC. Crude 2-pent-2-ynyloxy-tetrahydro-pyran (12.4 g) was obtained with a purity of 90.1% (94.3% yield based on 2-prop-2-ynyloxy-tetrahydropyran).

Provenance & Evidence