Bromine → HCID 9998787, compound

HRID 2113650Notes

Reaction equation

HRID 2113650 reaction equation
[Br:1]Br.[CH2:3]([C@@:7]12[C@H:19]([CH2:20][CH2:21][CH3:22])[C:18](=[O:23])[CH:17]=[C:8]1[C:9]1[CH:10]=[CH:11][C:12]([OH:16])=[CH:13][C:14]=1[CH2:15]2)[CH2:4][CH2:5][CH3:6].C([O-])(O)=O.[Na+]>C(Cl)(Cl)(Cl)Cl.C(Cl)Cl>[Br:1][C:17]1[C:18](=[O:23])[C@@H:19]([CH2:20][CH2:21][CH3:22])[C@@:7]2([CH2:3][CH2:4][CH2:5][CH3:6])[CH2:15][C:14]3[CH:13]=[C:12]([OH:16])[CH:11]=[CH:10][C:9]=3[C:8]=12

Participants

6

Reactant 3

HCID 24408BromineHCID 516892Sodium BicarbonateHCID 58604044HCID 58604044, compound

Product 1

HCID 9998787HCID 9998787, compound

Reagents, catalysts & solvents 2

HCID 5943Carbon TetrachlorideSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
2.5 °C

Procedure

Bromine (0.0072 mL, 0.14 mmol) was added to an ice-cold mixture of (rac)-(1S,8aR)-8a-butyl-6-hydroxy-1-propyl-8,8a-dihydrocyclopenta[a]inden-2(1H)-one (40 mg, 0.14 mmol) and NaHCO3 (59 mg, 0.70 mmol) in CCl4 (0.48 mL). The resulting mixture was sonicated for 20 seconds and then stirred at 0-5° C. for 70 minutes. The mixture was diluted with CH2Cl2 (30 mL) and washed with water (30 mL), and the aqueous phase was back-extracted with CH2Cl2 (2×10 mL). The combined organics were washed with saturated aqueous Na2S2O3, dried over MgSO4, filtered, and evaporated under vacuum. The residue was purified by Biotage™ (Charlottesville, Va.) flash chromatography on a 12S (1.2×7.5 cm) silica gel column, eluting with 10:1 hexane-EtOAc, to give a clear oil. This material was further purified by preparative layer chromatography on a 0.1×20×20 cm silica gel GF plate (Analtech, Newark, Del.), developing twice with 5:1 hexane-EtOAc. The major UV visible band provided (rac)-(1S,8aR)-3-bromo-8a-butyl-6-hydroxy-1-propyl-8,8a-dihydrocyclopenta[a]inden-2(1H)-one as an oil.

Workup

  1. customThe resulting mixture was sonicated for 20 seconds
  2. washwashed with water (30 mL)
  3. extractionthe aqueous phase was back-extracted with CH2Cl2 (2×10 mL)
  4. washThe combined organics were washed with saturated aqueous Na2S2O3
  5. dry with materialdried over MgSO4
  6. filtrationfiltered
  7. customevaporated under vacuum
  8. customThe residue was purified by Biotage™ (Charlottesville, Va.) flash chromatography on a 12S (1.2×7.5 cm) silica gel column
  9. washeluting with 10:1 hexane-EtOAc
  10. customto give a clear oil
  11. customThis material was further purified by preparative layer chromatography on a 0.1×20×20 cm silica gel GF plate (Analtech, Newark, Del.)

Sources & evidence

ORD record
ord-079057216aa84a439d6ae9aa1e584069
Source dataset
uspto-grants-2008_10
Patent number
US07432284B2

Reaction notes

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