反应详情

温度

60 °C

The amine of Example 5 (500 mg, 0.70mmol) was dissolved in water (20 mL), and the pH was adjusted to 11.5 with 1M LiOH. The reaction mixture was heated at 60° C., and three aliquots of 4,4-dimethyl-3,5,8-trioxabicyclo[5.1.0]octane (see J. Org. Chem. 41: 2469 (1976)) (180 μL) were added at 8 hour intervals. Heating was continued for 48 hours. After cooling, the mixture was treated with 10% HCl, refluxed for 2 hours, and loaded on an AG1-X8 cation exchange column [40 mL (OAc form)]. The column was washed with water (500 mL), and the product was eluted with 1M CH2COOH. The fractions containing the product were combined and evaporated to a white powder (420 mg (81.4%)). 1H NMR (D2O, 355° K) δ 1.6-2.0 (br mult., 4H), 2.7-3.8 (br mult. 54H). 13C NMR (D2O): 23.5, 25.2, 25.5, 44.5, 44.9, 49.8, 50.3, 54.9, 55.1, 57.2, 58.0, 58.7, 59.5, 61.6, 62.2, 62.9, 68.6, 69.1, 169.6, 170.2, 174.0. MS (FAB): m/e 927.5 (MH+). Anal. Calcd for C38H70N8O18 8H2O: C, 43.92; H, 8.34; N, 10.78. Found C, 43.94; H, 7.65; N, 10.78.

1. temperatureHeating
2. temperatureAfter cooling
3. temperaturerefluxed for 2 hours
4. washThe column was washed with water (500 mL)
5. washthe product was eluted with 1M CH2COOH
6. additionThe fractions containing the product
7. customevaporated to a white powder (420 mg (81.4%))