Hydrochloric Acid → HCID 178419183, compound

HRID 556194Notes

Reaction equation

HRID 556194 reaction equation
[Cl-].[Ce+3].[Cl-].[Cl-].[BH4-:5].[Na+].[C:7]([C:11]1[CH:12]=[C:13]([PH:21](=O)[C:22]2[CH:27]=[C:26]([C:28]([CH3:31])([CH3:30])[CH3:29])[CH:25]=[C:24]([C:32]([CH3:35])([CH3:34])[CH3:33])[CH:23]=2)[CH:14]=[C:15]([C:17]([CH3:20])([CH3:19])[CH3:18])[CH:16]=1)([CH3:10])([CH3:9])[CH3:8].[H-].[Al+3].[Li+].[H-].[H-].[H-].Cl>C1COCC1.O.C1(C)C=CC=CC=1>[C:17]([C:15]1[CH:14]=[C:13]([PH:21][C:22]2[CH:27]=[C:26]([C:28]([CH3:31])([CH3:30])[CH3:29])[CH:25]=[C:24]([C:32]([CH3:35])([CH3:34])[CH3:33])[CH:23]=2)[CH:12]=[C:11]([C:7]([CH3:10])([CH3:9])[CH3:8])[CH:16]=1)([CH3:18])([CH3:19])[CH3:20].[BH3:5]

Participants

9

Reactant 5

HCID 313Hydrochloric AcidHCID 24636Cerium(III) chlorideHCID 4311764Sodium borohydrideHCID 21226445Aluminium lithium hydrideHCID 178441221HCID 178441221, compound

Product 1

HCID 178419183HCID 178419183, compoundYield 72.7%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 1140TolueneSolventHCID 8028TetrahydrofuranSolvent

Procedure

Under a nitrogen stream, a solution of cerium chloride (4.88 g, 3.00 equivalents) in THF (40 mL) was stirred at room temperature (25° C.) for 30 min. Sodium borohydride (0.75 g, 3.00 equivalents) was added, and the mixture was stirred at room temperature for 1 hr. Then bis(3,5-di-tert-butylphenyl)phosphine oxide (2.81 g, 6.6 mmol) synthesized in Reference Example 16 and lithium aluminum hydride (0.39 g, 1.23 equivalents) were successively added at −9° C. and the mixture was stirred for 1.5 hrs. Toluene (20 mL) was added at 4° C., 6M-HCl (6 mL) was added and water (10 mL) was added at 4° C., and the mixture was stirred at room temperature for 30 min. The reaction mixture was partitioned, and the organic layer was dried over anhydrous magnesium sulfate, filtered by gravity, and passed through a membrane filter (0.2 μm) under reduced pressure. To the filtrate was added a borane-THF complex (7 mL, 1.08 equivalents) at room temperature and the mixture was stirred for 16 hrs. and concentrated under reduced pressure. To the concentrate was added a borane-THF complex (10 mL, 1.55 equivalents) at room temperature and the mixture was concentrated under reduced pressure. Toluene (10 mL) was added to the residue for dissolution and the mixture was purified by silica gel column chromatography (silica gel 25 g, toluene). The effective fraction was concentrated under reduced pressure. The residue was recrystallized from n-hexane and dried (reduced pressure, 40° C.) to give the title compound (2.03 g, white powder). yield 72.7%. melting point: 135.4° C.

Workup

  1. additionwere successively added at −9° C.
  2. stirringthe mixture was stirred for 1.5 hrs
  3. stirringthe mixture was stirred at room temperature for 30 min
  4. customThe reaction mixture was partitioned
  5. dry with materialthe organic layer was dried over anhydrous magnesium sulfate
  6. filtrationfiltered by gravity
  7. filtrationfilter (0.2 μm) under reduced pressure
  8. additionTo the filtrate was added a borane-THF complex (7 mL, 1.08 equivalents) at room temperature
  9. stirringthe mixture was stirred for 16 hrs
  10. concentrationand concentrated under reduced pressure
  11. additionTo the concentrate was added a borane-THF complex (10 mL, 1.55 equivalents) at room temperature
  12. concentrationthe mixture was concentrated under reduced pressure
  13. additionToluene (10 mL) was added to the residue for dissolution
  14. customthe mixture was purified by silica gel column chromatography (silica gel 25 g, toluene)
  15. concentrationThe effective fraction was concentrated under reduced pressure
  16. customThe residue was recrystallized from n-hexane
  17. customdried (reduced pressure, 40° C.)

Sources & evidence

ORD record
ord-71474a59704748e587a429b9b7891770
Source dataset
uspto-grants-2011_11
Patent number
US08053604B2

Reaction notes

Loading…