반응 #554635

ord-5596620960c34ab1b1f43852351e4fcd

반응 방정식

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
수율 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
수율 78.5%

반응물

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

시약

없음

용매

C1CCOC1
tetrahydrofuran

반응 조건

온도
23°CELSIUS
상세 조건
See reaction.notes.procedure_details.

후처리

  1. 1
    추출extracted with ethyl acetate
  2. 2
    세척the combined organic extracts are washed with saturated sodium chloride solution
  3. 3
    건조dried over sodium sulfate
  4. 4
    기타The residue obtained
  5. 5
    여과after filtration and solvent removal
  6. 6
    workup.ADDITIONtreated with 80 ml of a 30% hydrogen peroxide solution
  7. 7
    온도with cooling
  8. 8
    workup.ADDITIONafter 20 minutes poured
  9. 9
    온도with cooling into 600 ml of a semi-concentrated sodium thiosulfate solution
  10. 10
    추출This is extracted with ethyl acetate
  11. 11
    세척the combined organic extracts are washed with saturated sodium chloride solution
  12. 12
    건조dried over sodium sulfate
  13. 13
    기타The residue obtained
  14. 14
    여과after filtration and solvent removal
  15. 15
    기타is purified by recrystallisation

실험 절차

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.

출처

DOI: 10.6084/m9.figshare.5104873.v1특허: US08623850B2uspto-grants-2014_01