反应详情

A solution of 1-chloro-3-methoxy-propane (10.0 g, 92 mmol) in abs. ether (15 ml) was added dropwise, under an argon atmosphere and with intermittent heating, to magnesium (10.0 g, 92 mmol) and I2 in abs. diethyl ether (30 ml). Then the mixture was stirred under reflux for 60 min., following which the magnesium had not dissolved completely. While cooling with ice, a solution of 8-dimethylamino-1,4-dioxa-spiro[4.5]decane-8-carbonitrile B-1 (9.68 g, 46 mmol) in abs. THF (30 ml) was added dropwise. A viscous precipitate formed, and 100 ml of THF were then added for the purpose of better mixing. The mixture was stirred for 24 h at room temperature. 20% NH4Cl solution (100 ml) and water (120 ml) were added to the mixture, while cooling with ice, the organic phase was separated and the aqueous phase was extracted with ether (3×120 ml). The combined organic phases were washed with saturated NaCl solution (120 ml) and water (120 ml), dried over Na2SO4 and concentrated in vacuo. The crude yield was 10.8 g of brown oil. 9.8 g of crude product were purified by flash chromatography with CHCl3/MeOH (50:120:19:1).

1. temperatureunder reflux for 60 min.
2. dissolutionhad not dissolved completely
3. temperatureWhile cooling with ice
4. customA viscous precipitate formed
5. additionof better mixing
6. stirringThe mixture was stirred for 24 h at room temperature
7. temperaturewhile cooling with ice
8. customthe organic phase was separated
9. extractionthe aqueous phase was extracted with ether (3×120 ml)
10. washThe combined organic phases were washed with saturated NaCl solution (120 ml) and water (120 ml)
11. dry with materialdried over Na2SO4
12. concentrationconcentrated in vacuo
13. custom9.8 g of crude product were purified by flash chromatography with CHCl3/MeOH (50:120:19:1)