反应详情

A mixture of morphine (23.63 g, 83 mmol), NaHCO3 (28.2 g, 336 mmol), Ac2O (8.69 g, 85 mmol) in toluene (500 ml) and CH3CN (900 ml) was heated at reflux for 21 hrs. The reaction mixture was evaporated to dryness in vacuo. To the residue was added water (80 ml) and extracted with chloroform (500 ml). The extracts were dried, combined and evaporated to dryness in vacuo to obtain a residue, which was chromatographed on silica gel (column: d=6 cm, l=8 cm, packed with 141 g of silica gel; solvent system: 5-10% MeOH in CH2Cl2) to yield 3-acetylmorphine (27 g,100% yield). IR (KBr)(ν, cm-1): 3500 (m, sharp, --OH), 1750 (s, sharp, AcO); NMR (δH)(CDCl3): 6.73 (1, d, J, 8.1, 2-H), 6.57 (1, d, J, 8.1, 1-H), 5.74 (1, dm, J, 10.1, 7-H), 5.25 (1, dm, J, 9.9, 8-H), 4.91 (1, d, J, 6.9, 5-H), 4.25-4.10 (1, m, 6-H), 3.50-3.35 (1, m, 9-H), 3.05 (1, d, J, 19.1, 10-Hβ), 2.8-2.7 (1, m, 14-H), 2.85-2.60 (1, m, 16-He), 2.50-2.25 (1, m, 16-Ha), 2.45 (3, s, NCH3), 2.5-2.2 (1, m, 10-Hα), 2.28 (3, s, AcO), 2.06 (1, td, J, 12.1 & 5.0, 15-Ha), 2.0-1.85 (1, m, 15-He).

1. temperaturewas heated
2. temperatureat reflux for 21 hrs
3. customThe reaction mixture was evaporated to dryness in vacuo
4. additionTo the residue was added water (80 ml)
5. extractionextracted with chloroform (500 ml)
6. customThe extracts were dried
7. customevaporated to dryness in vacuo
8. customto obtain a residue, which
9. customwas chromatographed on silica gel (column: d=6 cm, l=8 cm, packed with 141 g of silica gel; solvent system: 5-10% MeOH in CH2Cl2)