Sulfuric acid magnesium salt (1:1) → HCID 69220530, compound

HRID 132854Notes

Reaction equation

HRID 132854 reaction equation
[C:1]([N:20]1[CH2:25][CH2:24][CH2:23][C:22](=O)[CH2:21]1)([C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1)([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.S([O-])([O-])(=O)=O.[Mg+2].[NH:33]1CCCC1.C(O[CH:41]=[CH:42][C:43](=O)[C:44]([F:47])([F:46])[F:45])C.C([O-])(=O)C.[NH4+]>O1CCCC1>[F:45][C:44]([F:47])([F:46])[C:43]1[CH:42]=[CH:41][C:23]2[CH2:24][CH2:25][N:20]([C:1]([C:14]3[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=3)([C:8]3[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=3)[C:2]3[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=3)[CH2:21][C:22]=2[N:33]=1

Participants

7

Reactant 5

HCID 24083Sulfuric acid magnesium salt (1:1)HCID 31268PyrrolidineHCID 517165Ammonium AcetateHCID 27803954-Ethoxy-1,1,1-trifluoro-3-buten-2-oneHCID 227070511-Tritylpiperidin-3-one

Product 1

HCID 69220530HCID 69220530, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A mixture of N-trityl-3-piperidone (1.22 g, 3.6 mmol), magnesium sulfate (2.70 g) and pyrrolidine (0.36 mL, 4.3 mmol) in 10 mL of tetrahydrofuran was stirred at room temperature for 72 h. The reaction mixture was filtered, and the filtrate was concentrated under reduced pressure. The resultant crude enamine was dissolved in 13 mL of dry dioxane, cooled to approximately 10° C. and treated dropwise with 4-ethoxy-1,1,1-trifluoro-3-buten-2-one (0.61 mL, 4.3 mmol). The resultant orange solution was allowed to warm to room temperature overnight. Ammonium acetate (0.60 g) was added to the blood-red solution, and the mixture was heated at reflux for 2.5 h, cooled to room temperature and concentrated under reduced pressure. The residue was stirred with 100 mL of dry ether, filtered through a pad of Celite, and concentrated under reduced pressure. The resultant dark red gum was purified by flash chromatography (silica gel; 3% ethyl acetate/hexanes as eluant) to afford impure product. A portion (147 mg) of this material was further purified by preparative TLC (silica gel; 5% ethyl acetate/hexanes as eluant) to afford the title compound as a light yellow foam. LC/MS 365.2 (M+1).

Workup

  1. filtrationThe reaction mixture was filtered
  2. concentrationthe filtrate was concentrated under reduced pressure
  3. dissolutionThe resultant crude enamine was dissolved in 13 mL of dry dioxane
  4. temperaturecooled to approximately 10° C.
  5. temperatureto warm to room temperature overnight
  6. temperaturethe mixture was heated
  7. temperatureat reflux for 2.5 h
  8. temperaturecooled to room temperature
  9. concentrationconcentrated under reduced pressure
  10. stirringThe residue was stirred with 100 mL of dry ether
  11. filtrationfiltered through a pad of Celite
  12. concentrationconcentrated under reduced pressure
  13. customThe resultant dark red gum was purified by flash chromatography (silica gel; 3% ethyl acetate/hexanes as eluant)
  14. customto afford impure product
  15. customA portion (147 mg) of this material was further purified by preparative TLC (silica gel; 5% ethyl acetate/hexanes as eluant)

Sources & evidence

ORD record
ord-391b868f09bc46a1b71240b48f06877a
Source dataset
uspto-grants-2008_06
Patent number
US07388019B2

Reaction notes

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