Piperonal → HCID 23050471, compound

HRID 1651803Notes

Reaction equation

HRID 1651803 reaction equation
[C:1]([O:5][CH3:6])(=[O:4])[C:2]#[CH:3].C([Li])CCC.[CH2:12]1[O:22][C:21]2[CH:20]=[CH:19][C:16]([CH:17]=[O:18])=[CH:15][C:14]=2[O:13]1.[Cl-].[NH4+]>O1CCCC1>[OH:18][CH:17]([C:16]1[CH:19]=[CH:20][C:21]2[O:22][CH2:12][O:13][C:14]=2[CH:15]=1)[C:3]#[C:2][C:1]([O:5][CH3:6])=[O:4]

Participants

6

Reactant 4

HCID 8438PiperonalHCID 13536Methyl propiolateHCID 25517Ammonium ChlorideHCID 178418339Butyllithium

Product 1

HCID 23050471HCID 23050471, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A solution of 5 ml (60 mmol) of methyl propiolate in 60 ml of tetrahydrofuran was treated at -78° under argon with 37.5 ml of n-butyllithium (1.6M in hexane). The mixture was stirred at -78° for 10 minutes and then a solution of 9 g 60 mmol) of 3,4 -methylenedioxybenzaldehyde in 60 ml of tetrahydrofuran was added within 30 minutes. The reaction mixture was stirred at -78° for a further 20 minutes, then brought to room temperature and treated with 80 ml of saturated ammonium chloride solution. The aqueous phase was extracted twice with ether. The combined organic phases were washed in succession with saturated sodium chloride solution and with water, dried over sodium sulphate and concentrated. The residue was purified by flash chromatography on 500 g of silica gel (elution agent methylene chloride/ethyl acetate 9:1). There was obtained methyl 4-hydroxy-4-[3,4-(methylenedioxy) phenyl]-2-butynoate as a brown oil.

Workup

  1. stirringThe reaction mixture was stirred at -78° for a further 20 minutes
  2. custombrought to room temperature
  3. extractionThe aqueous phase was extracted twice with ether
  4. washThe combined organic phases were washed in succession with saturated sodium chloride solution and with water
  5. dry with materialdried over sodium sulphate
  6. concentrationconcentrated
  7. customThe residue was purified by flash chromatography on 500 g of silica gel (elution agent methylene chloride/ethyl acetate 9:1)

Sources & evidence

ORD record
ord-ae8b61d84d2b459c9f807d23b06a7937
Source dataset
uspto-grants-1990_05
Patent number
US04929741

Reaction notes

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