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HRID653338

反应详情

EQUATION

反应方程式

HRID 653338 的结构方程式

REACTANTS

反应物

3
结构：NN.O
HCID24654

Hydrazine hydrate (1:1)

H6N2O

结构：C[O-].[Na+]
HCID10942334

Methanol, sodium salt

CH3NaO

结构：CCCCCCCCCCCCCCCCCCSCCO[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]1N1C(=O)c2ccccc2C1=O
HCID18608319

未命名化合物

PRODUCTS

生成物

1
结构：CCCCCCCCCCCCCCCCCCSCCO[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
HCID86741645

未命名化合物

收率 52.9%

AUXILIARIES

试剂、催化剂与溶剂

2
结构：CO
溶剂HCID887

Methanol

CH4O

2 次

结构：C1CCOC1
溶剂HCID8028

Tetrahydrofuran

C4H8O

PROCEDURE

实验过程

Compound 80 (1.46 g, 1.1 mmol) was dissolved in a mixure of methanol (75 ml) and tetrahydrofuran (10 ml) by warming. The clear solution was rapidly cooled to ~40° C. and methanolic sodium methoxide (0.2 M, 5 ml) was added. The mixture was stirred at room temperature for 5 h, after which time the deacetylation was complete. (TLC; SiO2,chloroform:methanol:water 65:35:10, lower phase), neutralized by addition of acidic ion-exchange resin (Duolite C-26), filtered and evaporated. The residue was re-dissolved in refluxing methanol (50 ml) and hydrazine hydrate (0.5 g, 10 mmol) was added. The reflux was continued for 17.5 h, whereafter the solvent was evaporated. The residue was acetylated by stirring for 22 h at room temperature in a mixture of pyridine and acetic anhydride (1:1, 50 ml). After evaporation, the residue was subjected to chromatography (SiO2 -column, 5×18 cm, ethyl acetate: isooctane gradient: 2:1-4:1-ethyl acetate) which gave amorphous 83 (0.72 g, 52%) with [α]D21 +32° (c 1.1, chloroform). 1H-NMR (CDC13, Me4Si) δ 5.67 (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"), 5.23-5.01 (3H, H2', H2" and H3), 4.99 (d, 1H, J=3.5, H1"), 4.75 (dd, 1H, J=11 and 2.5 Hz, H3') 4.58-4.37 (5H, inter alia H1and H1'), 4.54 and 4.49 (2d, each 1H, J=8 Hz each, H1 and H1'), 4.23-3.90 (7H), 3.85-3.55 (4H), 2.69 (t, 2H, J=7 Hz, OCH2CH2S), 2.51 (t, 2H, J=7 Hz, SCH2), 2.13, 2.12, 2.11, 2.08 (4s, each 3H, MeCO), 2.075, 2.05 (2s, each 6H, MeCO), 1.99, 1.97 (2s, each 3H, MeCO), 1.66-1.20, 0.88 (t, 3H, J=6.5 Hz, CH3CH2). 13C-NMR (CDC13, Me4Si) δ 170.6 (2C), 170.4 (3C), 170.2, 170.1, 169.6, 169.0, 101.1, 101.0 (d, J each 160 Hz, C1 and C1'), 99.6 (d, J=172 Hz, C1"), 76.9, 75.9, 72.7, 72.6 (2C), 71.8, 69.1 (OCH2CH2), 68.9, 68.7, 67.8, 67.1, 67.0, 62.4 (CH2), 61.3 (CH2), 60.2 (CH2), 53.3 (C2), 32.5-28.8, 23.3 (CH3CONH), 22.7 (CH2), 20.9-20.5, 14.1.

WORKUP

后处理

  1. temperatureby warming
  2. temperatureThe clear solution was rapidly cooled to ~40° C.
  3. filtrationfiltered
  4. customevaporated
  5. dissolutionThe residue was re-dissolved
  6. additionwas added
  7. waitThe reflux was continued for 17.5 h, whereafter the solvent
  8. customwas evaporated
  9. stirringby stirring for 22 h at room temperature in a mixture of pyridine and acetic anhydride (1:1, 50 ml)
  10. customAfter evaporation