反应 #554635

ord-5596620960c34ab1b1f43852351e4fcd

反应方程式

COc1ccc2c(c1)CC[C@@H]1[C@@H]2CC[C@]2(C)[C@@H](O)C=C[C@@H]12
3-methoxy-17β-hydroxyestra-1,3,5(10),15-tetraene
c1ccc(P(c2ccccc2)c2ccccc2)cc1
triphenylphosphine
O=C(O)c1ccc([N+](=O)[O-])cc1
4-nitrobenzoic acid
CC(C)OC(=O)N=NC(=O)OC(C)C
diisopropyl azodicarboxylate
[Cl-].[Na+]
sodium chloride
→
COc1ccc2c(c1)CC[C@@H]1[C@@H]2CC[C@]2(C)C(OC(=O)c3ccc([N+](=O)[O-])cc3)C=C[C@@H]12
title compound
收率 78.5%
COc1ccc2c(c1)CC[C@@H]1[C@@H]2CC[C@]2(C)C(OC(=O)c3ccc([N+](=O)[O-])cc3)C=C[C@@H]12
3-Methoxy-estra-1,3,5(10),15-tetraen-17-yl 4-nitrobenzoate
收率 78.5%

反应物

COc1ccc2c(c1)CC[C@@H]1[C@@H]2CC[C@]2(C)[C@@H](O)C=C[C@@H]12
3-methoxy-17β-hydroxyestra-1,3,5(10),15-tetraene
c1ccc(P(c2ccccc2)c2ccccc2)cc1
triphenylphosphine
O=C(O)c1ccc([N+](=O)[O-])cc1
4-nitrobenzoic acid
CC(C)OC(=O)N=NC(=O)OC(C)C
diisopropyl azodicarboxylate
[Cl-].[Na+]
sodium chloride

试剂

无

溶剂

C1CCOC1
tetrahydrofuran

反应条件

温度
23°CELSIUS
详细条件
See reaction.notes.procedure_details.

后处理

  1. 1
    萃取extracted with ethyl acetate
  2. 2
    洗涤the combined organic extracts are washed with saturated sodium chloride solution
  3. 3
    干燥dried over sodium sulfate
  4. 4
    其他The residue obtained
  5. 5
    过滤after filtration and solvent removal
  6. 6
    workup.ADDITIONtreated with 80 ml of a 30% hydrogen peroxide solution
  7. 7
    温度with cooling
  8. 8
    workup.ADDITIONafter 20 minutes poured
  9. 9
    温度with cooling into 600 ml of a semi-concentrated sodium thiosulfate solution
  10. 10
    萃取This is extracted with ethyl acetate
  11. 11
    洗涤the combined organic extracts are washed with saturated sodium chloride solution
  12. 12
    干燥dried over sodium sulfate
  13. 13
    其他The residue obtained
  14. 14
    过滤after filtration and solvent removal
  15. 15
    其他is purified by recrystallisation

实验过程

The solution of 43.9 g of 3-methoxy-17β-hydroxyestra-1,3,5(10),15-tetraene in 1.61 tetrahydrofuran is treated with 121 g of triphenylphosphine, 27.1 g of 4-nitrobenzoic acid and 30.9 ml of diisopropyl azodicarboxylate and stirred at 23° C. for 2 hours. This is treated with saturated sodium chloride solution, extracted with ethyl acetate, and the combined organic extracts are washed with saturated sodium chloride solution and dried over sodium sulfate. The residue obtained after filtration and solvent removal is taken up 1.2 l acetone, treated with 80 ml of a 30% hydrogen peroxide solution with cooling, and after 20 minutes poured with cooling into 600 ml of a semi-concentrated sodium thiosulfate solution. This is extracted with ethyl acetate, and the combined organic extracts are washed with saturated sodium chloride solution and dried over sodium sulfate. The residue obtained after filtration and solvent removal is purified by recrystallisation. 52.5 g of the title compound are isolated.

来源

DOI: 10.6084/m9.figshare.5104873.v1专利: US08623850B2uspto-grants-2014_01