Dimethylformamide → HCID 86719446, compound

HRID 1481634Notes

Reaction equation

HRID 1481634 reaction equation
[CH2:1]([Si:4]([CH2:18][CH:19]=[CH2:20])([CH2:15][CH:16]=[CH2:17])[CH2:5][CH2:6][CH2:7][C:8]1[CH:13]=[CH:12][C:11](Br)=[CH:10][CH:9]=1)[CH:2]=[CH2:3].C([Mg]Cl)(C)C.[Li]CCCC.CN(C)[CH:33]=[O:34].[Cl-].[NH4+]>C(OCC)C.C1COCC1>[CH2:1]([Si:4]([CH2:18][CH:19]=[CH2:20])([CH2:15][CH:16]=[CH2:17])[CH2:5][CH2:6][CH2:7][C:8]1[CH:13]=[CH:12][C:11]([CH:33]=[O:34])=[CH:10][CH:9]=1)[CH:2]=[CH2:3]

Participants

8

Reactant 5

HCID 6228DimethylformamideHCID 25517Ammonium ChlorideHCID 86719447HCID 86719447, compoundHCID 178418339ButyllithiumHCID 178418918HCID 178418918, compound

Product 1

HCID 86719446HCID 86719446, compoundYield 89%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-10 °C

Procedure

THF (50 ml) was added to 4-{3-(triallylsilyl)propyl}phenylbromide (3) (14.2 g, 40.6 mmol) under a nitrogen atmosphere, the mixture was cooled to around −10° C. with brine ice, and a solution of 2 M iPrMgCl (0.70 equivalent amount, 14.2 ml) and a solution of 1.67 M nBuLi (1.4 equivalent amount, 34.0 ml) were respectively added dropwise. The mixture was stirred at around −10° C. for 2 hours, N,N-dimethylformamide (DMF) (2 equivalent amount, 6.3 ml) was then added, and the mixture was stirred at room temperature for 14 hours. Diethyl ether was added to the reaction mixture, and the mixture was neutralized with a saturated aqueous solution of ammonium chloride. The aqueous layer was extracted with diethyl ether, and the combined organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, filtered, and concentrated under a reduced pressure to give a crude product. The crude product was purified by separating by silica gel column chromatography (elution solvent: hexane/ethyl acetate=20/1) to give 4-{3-(triallylsilyl)propyl}benzaldehyde (4) (yield amount: 11.0 g, yield: 89%), as shown in the following chemical reaction formula.

Workup

  1. stirringthe mixture was stirred at room temperature for 14 hours
  2. extractionThe aqueous layer was extracted with diethyl ether
  3. washthe combined organic layer was washed with saturated brine
  4. dry with materialdried over anhydrous magnesium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated under a reduced pressure
  7. customto give a crude product
  8. customThe crude product was purified
  9. customby separating by silica gel column chromatography (elution solvent: hexane/ethyl acetate=20/1)

Sources & evidence

ORD record
ord-fa7f68c3469e41489d69e9f58183d70e
Source dataset
uspto-grants-2016_08
Patent number
US09409929B2

Reaction notes

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