Hydrochloric Acid → 2-Formyl-17beta-estradiol

HRID 343302

반응식

HRID 343302 반응식
[CH3:1][C@@:2]12[C@@H:18]([OH:19])[CH2:17][CH2:16][C@H:15]1[C@H:14]1[C@@H:5]([C:6]3[CH:7]=[CH:8][C:9]([OH:20])=[CH:10][C:11]=3[CH2:12][CH2:13]1)[CH2:4][CH2:3]2.C1N2CN3CN(C2)CN1C3.FC(F)(F)[C:33](O)=[O:34].[C:38](=O)([O-])[O-:39].[K+].[K+].Cl>CO.CCOC(C)=O.O>[OH:20][C:9]1[C:8]([CH:33]=[O:34])=[CH:7][C:6]2[C@@H:5]3[C@H:14]([C@H:15]4[C@@:2]([CH2:3][CH2:4]3)([CH3:1])[C@@H:18]([OH:19])[CH2:17][CH2:16]4)[CH2:13][CH2:12][C:11]=2[CH:10]=1.[OH:20][C:9]1[CH:8]=[CH:7][C:6]2[C@@H:5]3[C@H:14]([C@H:15]4[C@@:2]([CH2:3][CH2:4]3)([CH3:1])[C@@H:18]([OH:19])[CH2:17][CH2:16]4)[CH2:13][CH2:12][C:11]=2[C:10]=1[CH:38]=[O:39]

참가 물질

10

반응물 5

HCID 313Hydrochloric AcidHCID 4101HexamethylenetetramineHCID 5757EstradiolHCID 6422Trifluoroacetic acidHCID 11430Potassium Carbonate

생성물 2

HCID 99949802-Formyl-17beta-estradiol수율 13%HCID 117223424-Formyl-17beta-estradiol수율 4%

시약·촉매·용매 3

HCID 887Methanol용매HCID 962Water용매HCID 8857Ethyl Acetate용매

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온도
100 °C

실험 절차

To a mixture of estradiol (1, 13.6 g, 50 mmol) and hexamethylenetetramine (21.0 g, 150 mmol) was added trifluoroacetic acid (100 mL) at room temperature. The reaction mixture was stirred for 6 h at 100° C., poured into H2O (300 mL), and extracted with Et2O. The combined organic layers were washed with H2O, then with saturated aqueous NaCl, and dried (MgSO4). The desiccant was filtered and the solvent was evaporated at reduced pressure. The residue was dissolved in THF (50 mL) and MeOH (50 mL), potassium carbonate (6.9 g, 50 mmol) was added, and the mixture stirred for 1 h at room temperature. The reaction mixture was then diluted with EtOAc, acidified with 1N HCl, and extracted with EtOAc. The combined organic layers were washed with H2O, then with saturated aqueous NaCl, and dried (MgSO4). The desiccant was filtered and the solvent was evaporated at reduced pressure. The residue was purified by column chromatography (silica gel) using n-hexane:THF (5:1→3:1, v/v) to afford 1.91 g of 2a (13% yield), m.p. 219°-221° C., and 0.552 g of 2b (4% yield), m.p. 146°-147° C.

후처리

  1. extractionextracted with Et2O
  2. washThe combined organic layers were washed with H2O
  3. dry with materialwith saturated aqueous NaCl, and dried (MgSO4)
  4. filtrationThe desiccant was filtered
  5. customthe solvent was evaporated at reduced pressure
  6. dissolutionThe residue was dissolved in THF (50 mL)
  7. stirringthe mixture stirred for 1 h at room temperature
  8. extractionextracted with EtOAc
  9. washThe combined organic layers were washed with H2O
  10. dry with materialwith saturated aqueous NaCl, and dried (MgSO4)
  11. filtrationThe desiccant was filtered
  12. customthe solvent was evaporated at reduced pressure
  13. customThe residue was purified by column chromatography (silica gel)

출처 및 근거

ORD 기록
ord-64e0a4d0429e46eca901b4385d431ffc
출처 데이터셋
uspto-grants-1999_01
특허 번호
US05861388

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