反应详情

In the next step, a solution of dimethyl sulfoxide (DMSO) (35.3 ml, 0.491 mol) in methylene chloride (970 ml) is added dropwise, over a period of 2.5 hours at -60° C. under an atmosphere of nitrogen, to a solution of oxalyl chloride (44.7 ml, 0.491 mol) in methylene chloride (970 ml), and the mixture is stirred for a further five minutes. A solution of N-tosylsarcosyl-L-prolinol (80 g, 0.245 mol) in methylene chloride (950 ml) is then added dropwise to the mixture over a period of 75 minutes, and the mixture is stirred for a further thirty minutes. Triethylamine (348 ml, 2.45 mol) is then added dropwise thereto over a period of ten minutes, and the mixture is stirred for a further ten minutes. After brought back to room temperature, the mixture is washed with water (2 l×2) and the organic layer is concentrated to dryness under reduced pressure. The residue is dissolved in ethanol (320 ml), and the solution is vigorously stirred for 15 minutes after addition of a saturated aqueous solution of sodium hydrogen carbonate (250 ml) and water (438 ml). The ethanol is then distilled off under reduced pressure, and water (600 ml) is added to the residue. The mixture is extracted with chloroform (300 ml) and ether (500 ml×2) and the organic layers are discarded. The aqueous layers are adjusted with potassium carbonate to a pH higher than 10 and extracted with chloroform. The organic layer is separated, washed successively with water (500 ml×2), 1N hydrochloric acid (500 ml) and water (500 ml), dried over anhydrous magnesium sulfate and concentrated to dryness under reduced pressure to give N-tosylsarcosyl-L-prolinal (49.5 g, 62.3%).

1. stirringthe mixture is stirred for a further thirty minutes
2. waitover a period of ten minutes
3. stirringthe mixture is stirred for a further ten minutes
4. customAfter brought back to room temperature
5. washthe mixture is washed with water (2 l×2)
6. concentrationthe organic layer is concentrated to dryness under reduced pressure
7. dissolutionThe residue is dissolved in ethanol (320 ml)
8. stirringthe solution is vigorously stirred for 15 minutes
9. additionafter addition of a saturated aqueous solution of sodium hydrogen carbonate (250 ml) and water (438 ml)
10. distillationThe ethanol is then distilled off under reduced pressure, and water (600 ml)
11. additionis added to the residue
12. extractionThe mixture is extracted with chloroform (300 ml) and ether (500 ml×2)
13. extractionextracted with chloroform
14. customThe organic layer is separated
15. washwashed successively with water (500 ml×2), 1N hydrochloric acid (500 ml) and water (500 ml)
16. dry with materialdried over anhydrous magnesium sulfate
17. concentrationconcentrated to dryness under reduced pressure