Hydrochloric Acid → HCID 178419220, compound

HRID 556186Notes

Reaction equation

HRID 556186 reaction equation
[Cl-].[Ce+3].[Cl-].[Cl-].[BH4-:5].[Na+].[F:7][C:8]1[CH:13]=[CH:12][C:11]([PH:14](=O)[C:15]2[CH:20]=[CH:19][C:18]([F:21])=[CH:17][CH:16]=2)=[CH:10][CH:9]=1.[H-].[Al+3].[Li+].[H-].[H-].[H-].Cl>C1COCC1.C1(C)C=CC=CC=1.O>[F:21][C:18]1[CH:19]=[CH:20][C:15]([PH:14][C:11]2[CH:12]=[CH:13][C:8]([F:7])=[CH:9][CH:10]=2)=[CH:16][CH:17]=1.[BH3:5]

Participants

9

Reactant 5

HCID 313Hydrochloric AcidHCID 24636Cerium(III) chlorideHCID 4311764Sodium borohydrideHCID 21226445Aluminium lithium hydrideHCID 178527031HCID 178527031, compound

Product 1

HCID 178419220HCID 178419220, compoundYield 20.5%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 1140TolueneSolventHCID 8028TetrahydrofuranSolvent

Procedure

Under an argon atmosphere, a solution of cerium chloride (9.31 g, 3.0 equivalents) in THF (25 mL) was stirred at room temperature (25° C.) for 30 min. Sodium borohydride (1.48 g, 3.1 equivalents) was added, and the mixture was stirred at room temperature for 1 hr. Then bis(4-fluorophenyl)phosphine oxide (3.0 g, 12.6 mmoL) synthesized in Reference Example 5 and lithium aluminum hydride (0.57 g, 1.2 equivalents) were successively added at 5° C. and the mixture was stirred at room temperature for 3 hrs. Water (10 mL) was added at 3° C. and then toluene (30 mL) and 6M-HCl (20 mL) were added and the mixture was stirred at room temperature for 30 min. The reaction mixture was partitioned, and the aqueous layer was extracted with toluene (20 mL). The combined organic layer was washed with 5% aqueous NaCl solution (20 mL). The organic layer was dried over anhydrous magnesium sulfate, filtered by gravity, and the filtrate was concentrated under reduced pressure. The residue was purified by column chromatography (alumina 25 g, n-hexane/ethyl acetate=20/1). The residue was recrystallized from heptane to give the title compound (0.61 g, white crystals). yield 20.4%. melting point: 71.7° C.

Workup

  1. additionwere successively added at 5° C.
  2. stirringthe mixture was stirred at room temperature for 3 hrs
  3. stirringthe mixture was stirred at room temperature for 30 min
  4. customThe reaction mixture was partitioned
  5. extractionthe aqueous layer was extracted with toluene (20 mL)
  6. washThe combined organic layer was washed with 5% aqueous NaCl solution (20 mL)
  7. dry with materialThe organic layer was dried over anhydrous magnesium sulfate
  8. filtrationfiltered by gravity
  9. concentrationthe filtrate was concentrated under reduced pressure
  10. customThe residue was purified by column chromatography (alumina 25 g, n-hexane/ethyl acetate=20/1)
  11. customThe residue was recrystallized from heptane

Sources & evidence

ORD record
ord-f49deba21ce142f0b684df98622496f7
Source dataset
uspto-grants-2011_11
Patent number
US08053604B2

Reaction notes

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