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HRID653339

反应详情

EQUATION

反应方程式

HRID 653339 的结构方程式

REACTANTS

反应物

2
结构：NN.O
HCID24654

Hydrazine hydrate (1:1)

H6N2O

结构：CC(=O)OC[C@H]1O[C@H](O[C@@H]2[C@H](OC(C)=O)[C@@H](OC(C)=O)[C@H](O[C@H]3[C@H](OC(C)=O)[C@@H](N4C(=O)c5ccccc5C4=O)[C@H](OCCBr)O[C@@H]3COC(C)=O)O[C@@H]2COC(C)=O)[C@H](OC(C)=O)[C@@H](OC(C)=O)[C@H]1OC(C)=O
HCID86741643

未命名化合物

PRODUCTS

生成物

1
结构：CCO[C@@H]1O[C@H](COC(C)=O)[C@@H](O[C@@H]2O[C@H](COC(C)=O)[C@H](O[C@H]3O[C@H](COC(C)=O)[C@H](OC(C)=O)[C@H](OC(C)=O)[C@H]3OC(C)=O)[C@H](OC(C)=O)[C@H]2OC(C)=O)[C@H](OC(C)=O)[C@H]1NC(C)=O
HCID88636952

未命名化合物

收率 28.6%

AUXILIARIES

试剂、催化剂与溶剂

3
结构：[Pd]
催化剂HCID23938

Palladium

Pd

结构：ClCCl
溶剂HCID6344

Dichloromethane

CH2Cl2

结构：C[O-].[Na+]
溶剂HCID10942334

Methanol, sodium salt

CH3NaO

PROCEDURE

实验过程

Compound 78 (0.65 g, 0.58 mmol) was hydrogenated (10% Pd/C, 0.31 g, 40 psi) in methanolic sodium methoxide (0.02M, 56 ml) at room temperature for 20 h, filtered and neutralized with Duolite C-26 (H+) resin. The mixture was filtered and concentrated and the residue was dissolved in methanol (20 ml) and hydrazine hydrate (1.7 g, 34 mmol), refluxed for 23 h and concentrated. The residue was acetylated (acetic anhydride:pyridine 1:1 50 ml) at room temperature for 18 h. Co-concentration with toluene gave a residue that was dissolved in dichloromethane (75 ml) and washed with water (50 ml). The water phase was extracted with dichloromethane (25 ml) and the combined organic extracts were washed with water (10 ml), dried (Na2SO4), and concentrated. The residue was chromatographed (SiO2 -column, 1.5×46 cm, ethyl acetate) to give crystalline 87 (158 mg, 28%) with mp 130°-133°, [α]D22 +41° (c 0.7, chloroform). 1H-NMR (CDCl3, Me4Si) δ 5.73 (d, 1H, J=9.5 Hz, NH), 5.58 (bd, 1H, J~3 Hz, H4"), 5.39 (dd, 1H, J=11 and 3 Hz, H3"), 5.19 (dd, 1H, J=11 and 3.5 Hz, H2"), 5.12 (dd, 1H, J=11 and 8 Hz, H2'), 5.10 (dd, 1H, J=9.5 and 8 Hz, H3), 5.00 (d, 1H, J=3.5 Hz, H1"), 4.76 (dd, 1H, J=11 and 2.5 Hz, H3'), 4.58-4.37 (5H, inter alia H1, H1'), 4.55 (d, 1H, J=8 Hz, H1 or H1'), 4.46 (d, 1H, J=7.5 Hz, H1 or H1'), 4.23-3.96 (6H), 3.95-3.73 (3H), 3.71-3.45 (2H), 2.14, 2.11, 2.106, 2.084, 2.079, 2.076, 2.06, 2.05, 1.99, 1.97, 1.19 (t, 3H, J=7 Hz, CH3CH2). 13C-NMR (CDCl3, Me4Si) δ 170.6 (2C), 170.51, 170.46 (2C), 170.4, 170.3, 170.1, 169.7, 169.1, 101.1 (d, J=164 Hz, C1 or C1'), 100.7 (d, J=160 Hz, C1 or C1'), 99.6 (d, J=174 Hz, C1"), 77.0, 76.1, 72.8, 72.7, 72.5, 71.9, 69.0, 68.7, 67.9, 67.1 (2C), 65.0 (CH2), 62.5 (CH2), 61.4 (CH2), 60.3 (CH2), 53.4 (C2), 23.2-20.5, 15.1 (CH3CH2).

WORKUP

后处理

  1. customat room temperature
  2. customfor 20 h
  3. filtrationfiltered
  4. filtrationThe mixture was filtered
  5. concentrationconcentrated
  6. dissolutionthe residue was dissolved in methanol (20 ml)
  7. concentrationconcentrated
  8. customat room temperature
  9. customfor 18 h
  10. concentrationCo-concentration with toluene
  11. customgave a residue that
  12. washwashed with water (50 ml)
  13. extractionThe water phase was extracted with dichloromethane (25 ml)
  14. washthe combined organic extracts were washed with water (10 ml)
  15. dry with materialdried (Na2SO4)
  16. concentrationconcentrated
  17. customThe residue was chromatographed (SiO2 -column, 1.5×46 cm, ethyl acetate)