反应详情

52 g (0.212 mol) of 1,11-diazido-3,6,9-trioxaundecane (1) were stirred with 480 ml of 5% aqueous HCl and a solution of 47.8 g (0.182 mol) PPh3 in 350 ml diethyl ether was added dropwise under stirring during a period of 45 minutes. After stirring for another 24 hours, the precipitate was filtered off and the separated aqueous layer was washed 3× with 100 mL portions of diethyl ether. Then, 41.4 g KOH were added to the aqueous layer (to pH 11) and the solution was allowed to stand at 4° C. for 16 hours. Any further precipitate was filtered off and the mixture was further basified by adding another 93 g of KOH. The product formed a second layer and was extracted 7× with 100 mL portions of DCM. The combined organic phases were dried over Na2SO4, filtered and concentrated by rotary evaporation to yield an amber oil, which was used without any further purification (35.7 g≅77% of theoretical yield). 1H-NMR (CDCl3): δ 3.68 (m, 10H), δ 3.54 (t, J=5 Hz, 2H), δ 3.39 (t, J=5 Hz, 2H), δ 2.86 (t, J=5 Hz, 2H), δ 1.49 (br, s, 2H). See Schwabacher, A. W. et al. (1998) J. Org. Chem. 63, 1727–1729.

1. stirringAfter stirring for another 24 hours
2. filtrationthe precipitate was filtered off
3. washthe separated aqueous layer was washed 3× with 100 mL portions of diethyl ether
4. additionThen, 41.4 g KOH were added to the aqueous layer (to pH 11)
5. waitto stand at 4° C. for 16 hours
6. filtrationAny further precipitate was filtered off
7. additionby adding another 93 g of KOH
8. customThe product formed a second layer
9. extractionwas extracted 7× with 100 mL portions of DCM
10. dry with materialThe combined organic phases were dried over Na2SO4
11. filtrationfiltered
12. concentrationconcentrated by rotary evaporation
13. customto yield an amber oil, which
14. customwas used without any further purification (35.7 g≅77% of theoretical yield)