Hydrochloric Acid → HCID 178419169, compound

HRID 556183Notes

Reaction equation

HRID 556183 reaction equation
[Cl-].[Ce+3].[Cl-].[Cl-].[BH4-:5].[Na+].[CH3:7][C:8]1[CH:13]=[CH:12][C:11]([PH:14](=O)[C:15]2[CH:20]=[CH:19][C:18]([CH3:21])=[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>[CH3:7][C:8]1[CH:9]=[CH:10][C:11]([PH:14][C:15]2[CH:20]=[CH:19][C:18]([CH3:21])=[CH:17][CH:16]=2)=[CH:12][CH:13]=1.[BH3:5]

Participants

9

Reactant 5

HCID 313Hydrochloric AcidHCID 24636Cerium(III) chlorideHCID 4311764Sodium borohydrideHCID 21226445Aluminium lithium hydrideHCID 178427273HCID 178427273, compound

Product 1

HCID 178419169HCID 178419169, compoundYield 51.7%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 1140TolueneSolventHCID 8028TetrahydrofuranSolvent

Procedure

Under an argon atmosphere, a solution of cerium chloride (7.89 g, 3.0 equivalents) in THF (20 mL) was stirred at room temperature (25° C.) for 30 min. Sodium borohydride (1.25 g, 3.1 equivalents) was added, and the mixture was stirred at room temperature for 1 hr. Then bis(4-methylphenyl)phosphine oxide (2.5 g, 0.011 moL) synthesized in Reference Example 8 and lithium aluminum hydride (0.494 g, 1.2 equivalents) were successively added at 5° C., and the mixture was stirred at room temperature for 17 hrs. Water (10 mL) was added at 3° C. and then toluene (20 mL) and 6M-HCl (20 mL) were added. The mixture was stirred at room temperature for 30 min. The reaction mixture was partitioned, and the aqueous layer was extracted with toluene (30 mL). The combined organic layer was washed successively with 5% aqueous NaHCO3 solution (20 mL) and 5% aqueous NaCl solution (20 mL). Then 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=10/1). The residue was recrystallized from heptane to give the title compound (1.28 g, white crystals). yield 51.0%. melting point: 78.6° C.

Workup

  1. additionwere successively added at 5° C.
  2. stirringthe mixture was stirred at room temperature for 17 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 (30 mL)
  6. washThe combined organic layer was washed successively with 5% aqueous NaHCO3 solution (20 mL) and 5% aqueous NaCl solution (20 mL)
  7. dry with materialThen the 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=10/1)
  11. customThe residue was recrystallized from heptane

Sources & evidence

ORD record
ord-1b86db9d48c141d0adc50ecae0627f6b
Source dataset
uspto-grants-2011_11
Patent number
US08053604B2

Reaction notes

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