Diisopropylamine → HCID 17861959, compound

HRID 1784449Notes

Reaction equation

HRID 1784449 reaction equation
C(NC(C)C)(C)C.C([Li])CCC.CCCCCC.[C:19]([O:22][CH2:23][CH3:24])(=[O:21])[CH3:20].[CH3:25][N:26]([CH3:40])[C:27](=[O:39])[O:28][C:29]1[CH:34]=[CH:33][C:32]([CH:35]=[O:36])=[C:31]([CH:37]=[CH2:38])[CH:30]=1.[Cl-].[NH4+]>O1CCCC1>[CH3:25][N:26]([CH3:40])[C:27]([O:28][C:29]1[CH:34]=[CH:33][C:32]([CH:35]([OH:36])[CH2:20][C:19]([O:22][CH2:23][CH3:24])=[O:21])=[C:31]([CH:37]=[CH2:38])[CH:30]=1)=[O:39]

Participants

8

Reactant 6

HCID 7912DiisopropylamineHCID 8058HexaneHCID 8857Ethyl AcetateHCID 25517Ammonium ChlorideHCID 17861984HCID 17861984, compoundHCID 178418339Butyllithium

Product 1

HCID 17861959HCID 17861959, compoundYield 99.8%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a solution of diisopropylamine (1.26 g, 12.5 mmol) in tetrahydrofuran (30 ml) was added 1.6M solution of n-butyllithium in hexane (7.20 ml, 11.5 mmol) at −20° C. with stirring, and the resulting mixture was stirred for 20 minutes at −20° C. under a nitrogen atmosphere. Subsequently, ethyl acetate (1.07 ml, 11.0 mmol) was added at −78° C., and the resulting mixture was stirred for 20 minutes at −78° C. under a nitrogen atmosphere. Subsequently, to the reaction mixture was added a solution of 4-formyl-3-vinyl-phenyl dimethylcarbamate (2.11 g, 9.62 mmol) obtained in step (c) of Example 192 in tetrahydrofuran at −78° C., and the resulting mixture was stirred for 30 minutes at −78° C. under a nitrogen atmosphere. After stirring, to the reaction mixture was added saturated aqueous ammonium chloride solution (40 ml), and the resulting mixture was extracted with ethyl acetate (40 ml×2). The organic layer was washed successively with water (40 ml×1) and saturated aqueous sodium chloride solution (40 ml×1), dried over anhydrous sodium sulfate, filtered, and evaporated in vacuo to afford the crude product. The crude product was purified by chromatography on a silica gel column using a mixed solvent of hexane and ethyl acetate (1:1-1:2) as the eluent to afford the title compound (2.95 g, yield: 99%) as a colorless oil.

Workup

  1. stirringthe resulting mixture was stirred for 20 minutes at −20° C. under a nitrogen atmosphere
  2. stirringthe resulting mixture was stirred for 20 minutes at −78° C. under a nitrogen atmosphere
  3. stirringthe resulting mixture was stirred for 30 minutes at −78° C. under a nitrogen atmosphere
  4. stirringAfter stirring, to the reaction mixture
  5. extractionthe resulting mixture was extracted with ethyl acetate (40 ml×2)
  6. washThe organic layer was washed successively with water (40 ml×1) and saturated aqueous sodium chloride solution (40 ml×1)
  7. dry with materialdried over anhydrous sodium sulfate
  8. filtrationfiltered
  9. customevaporated in vacuo
  10. customto afford the crude product
  11. customThe crude product was purified by chromatography on a silica gel column

Sources & evidence

ORD record
ord-fa43c8d32bb7464c940f3914b41e2b99
Source dataset
uspto-grants-2009_03
Patent number
US07504393B2

Reaction notes

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