Hydrogen Peroxide → 8-Hydroxy-2-phenyl-5,6,7,8-tetrahydroquinoline

HRID 1866048노트

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HRID 1866048 반응식
[C:1]1([C:7]2[CH:16]=[CH:15][C:14]3[CH2:13][CH2:12][CH2:11][CH2:10][C:9]=3[N:8]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.OO.C([O-])([O-])=[O:20].[Na+].[Na+].[OH-].[Na+]>C(O)(=O)C.CO.C([O-])([O-])=O.[K+].[K+].C(Cl)(Cl)Cl>[OH:20][CH:10]1[C:9]2[N:8]=[C:7]([C:1]3[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=3)[CH:16]=[CH:15][C:14]=2[CH2:13][CH2:12][CH2:11]1

참가 물질

9

반응물 4

HCID 784Hydrogen Peroxide2회HCID 10340Sodium CarbonateHCID 14798Sodium HydroxideHCID 111383402-Phenyl-5,6,7,8-tetrahydroquinoline

생성물 1

HCID 115431308-Hydroxy-2-phenyl-5,6,7,8-tetrahydroquinoline수율 74%

시약·촉매·용매 4

HCID 11430Potassium Carbonate촉매HCID 176Acetic Acid용매HCID 887Methanol용매HCID 6212Chloroform용매

실험 절차

To a stirred solution of 2-phenyl-5,6,7,8-tetrahydroquinoline (3.80 g, 18 mmol) in glacial acetic acid (10 mL) was added a 30 wt. % aqueous solution of H2O2 (2 mL) and the resulting mixture was stirred at 70° for 18 h; at this point, another portion of H2O2 solution (2 mL) was added and stirring was continued for 2 days. The solution was cooled to room temperature and Na2CO3 (10 g) and CHCl3 (20 mL) were added. The resulting mixture was allowed to sit 15 min then filtered and the aqueous phase was extracted with CHCl3 (3×20 mL); the organic fractions were then combined, dried (MgSO4) and concentrated. The residue was then taken up in acetic anhydride (20 mL) and heated at 90° C. for 4 h with stirring. Removal of the Ac2O under reduced pressure afforded a pale yellow oil which was taken up in methanol (30 mL) and treated with K2CO3 (100 mg, 0.72 mmol). The resulting mixture was stirred overnight. A solution of 4 N NaOH (10 mL) was added and the mixture was extracted with CHCl3 (3×20 mL), dried (MgSO4) and concentrated in vacuo. Purification of the crude product by column chromatography (silica gel, hexane/EtOAc 4:1) afforded 3.0 g of 8-hydroxy-2-phenyl-5,6,7,8-tetrahydroquinoline AMD 8786 (74% yield) as a white solid. 1H NMR (CDCl3) δ 1.78-1.81 (m, 2H), 1.97-2.02 (m, 1H), 2.31-2.33 (m, 1H), 2.76-2.79 (m, 2H), 4.43 (s, 1H), 4.71 (t, 1H, J=7 Hz), 7.37-7.46 (m, 4H), 7.52 (d, 1H, J=8 Hz), 7.96 (dd, 2H, J=9, 2 Hz); 13C NMR (CDCl3) δ 19.4, 27.8, 30.5, 69.0, 119.0, 126.5, 128.5, 128.7, 129.8, 137.6, 138.7, 154.0, 157.5. ES-MS m/z 226 (M+H).

후처리

  1. stirringstirring
  2. waitwas continued for 2 days
  3. waitto sit 15 min
  4. filtrationthen filtered
  5. extractionthe aqueous phase was extracted with CHCl3 (3×20 mL)
  6. dry with materialdried (MgSO4)
  7. concentrationconcentrated
  8. temperatureheated at 90° C. for 4 h
  9. stirringwith stirring
  10. customRemoval of the Ac2O under reduced pressure
  11. customafforded a pale yellow oil which
  12. stirringThe resulting mixture was stirred overnight
  13. extractionthe mixture was extracted with CHCl3 (3×20 mL)
  14. dry with materialdried (MgSO4)
  15. concentrationconcentrated in vacuo
  16. customPurification of the crude product by column chromatography (silica gel, hexane/EtOAc 4:1)

출처 및 근거

ORD 기록
ord-8f4416725bba451f9269e78dd2c623a7
출처 데이터셋
uspto-grants-2009_12
특허 번호
US07629337B2

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