Hydrochloric Acid → 2,2-dimethyl-6-chloromethyl-1,3-dioxin-4-one

Participants

Reaction Conditions

Reaction Steps

A solution of 2,2,6-trimethyl-1,3-dioxin-4-one (16.0 g, 0.11 mol) in THF (50 ml) was added dropwise over 20 min to a solution of lithium diisopropylamide (75 ml, 2.0 M solution in heptane/THF/ethylbenzene, 0.15 mol) at the temperature of −78° C. During the addition, a fine yellow suspension formed. Subsequently, the enolate solution was stirred at −78° C. for another 1 h and then cannulated to a solution of hexachloroethane (39 g, 0.16 mol) in THF (200 ml) at −50° C. over 30 min. The resulting reaction mixture was then allowed to warm slowly to −25° C., and poured into ice-cold aqueous 10% hydrochloric acid (200 ml). The organic layer extracted with ether was washed with brine, dried over sodium sulfate and concentrated under reduced pressure to afford 15.9 g of yellow oil. The product was used without further purification. 1H NMR (CDCl3, ppm): δ 5.57 (s, 1H), 4.00 (s, 2H), 1.96 (s, 6H).

Provenance & Evidence