反应详情

温度

-60 °C

70 ml of dichloromethane were placed in a reaction vessel, admixed with oxalyl chloride (8.4 g, 5.7 ml, 66 mmol) and cooled to −60° C. A solution of DMSO (10.2 g, 9.3 ml, 131 mmol) in 30 ml of dichloromethane was added dropwise to this mixture over a period of 10 minutes. The mixture was stirred for another 5 minutes. A solution of 2,5-bis(hydroxymethyl)-4′-hexyloxybiphenyl (10 g, 32 mmol) (cf. D1) in 70 ml of dichloromethane was then added dropwise over a period of 15 minutes (the reaction solution became turbid). It was stirred for another 10 minutes and triethylamine (15.9g, 21.8 ml, 157 mmol) was subsequently added dropwise. The reaction solution became yellow during this procedure and a precipitate was formed. The acetone/dry ice bath was removed and the mixture was stirred for 2 hours at RT. A light-colored solid was then floating on the yellow liquid phase. The mixture was admixed with 150 ml of water, stirred for another 10 minutes (solid entered solution), the organic phase was separated off, the aqueous phase was extracted twice with dichloromethane, the combined organic phases were subsequently washed three times with water, dried over Na2SO4, filtered and subsequently evaporated to dryness on a rotary evaporator. The yellow oil crystallized after some time at RT and was subsequently recrystallized from hexane. It took a relatively long time for the product to become solid: pale beige, microcrystalline powder, 5.67 g (57%), purity about 98%.

1. stirringIt was stirred for another 10 minutes
2. customa precipitate was formed
3. customThe acetone/dry ice bath was removed
4. stirringthe mixture was stirred for 2 hours at RT
5. stirringstirred for another 10 minutes (solid entered solution)
6. customthe organic phase was separated off
7. extractionthe aqueous phase was extracted twice with dichloromethane
8. washthe combined organic phases were subsequently washed three times with water
9. dry with materialdried over Na2SO4
10. filtrationfiltered
11. customsubsequently evaporated to dryness on a rotary evaporator
12. customThe yellow oil crystallized after some time at RT
13. customwas subsequently recrystallized from hexane