Methyl propiolate → HCID 23050473, compound

HRID 1651815Notes

Reaction equation

HRID 1651815 reaction equation
[C:1]([O:5][CH3:6])(=[O:4])[C:2]#[CH:3].C([Li])CCC.[CH3:12][S:13][C:14]1[CH:21]=[CH:20][C:17]([CH:18]=[O:19])=[CH:16][CH:15]=1.[Cl-].[NH4+]>O1CCCC1>[OH:19][CH:18]([C:17]1[CH:20]=[CH:21][C:14]([S:13][CH3:12])=[CH:15][CH:16]=1)[C:3]#[C:2][C:1]([O:5][CH3:6])=[O:4]

Participants

6

Reactant 4

HCID 13536Methyl propiolateHCID 25517Ammonium ChlorideHCID 769854-(Methylthio)benzaldehydeHCID 178418339Butyllithium

Product 1

HCID 23050473HCID 23050473, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A solution of 8.4 ml (0.1 mol) of methyl propiolate in 100 ml of tetrahydrofuran was treated at -78° under argon with 69 ml of n-butyllithium (1.6M in hexane). The mixture was stirred at -78° for 10 minutes and then a solution of 13 ml (0.1 mol) of 4-(methylthio)benzaldehyde in 100 ml of tetrahydrofuran was added within 40 minutes. The reaction mixture was stirred at -78° for a further 20 minutes, then brought to room temperature and treated with 150 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 1000 g of silica gel (elution agent methylene chloride/ether 4:1). There was obtained methyl 4-hydroxy-4-[4-(methylthio)phenyl]-2-butynoate as a red 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 The residue
  7. customwas purified by flash chromatography on 1000 g of silica gel (elution agent methylene chloride/ether 4:1)

Sources & evidence

ORD record
ord-3652ad74d61a4df68e2dffe46b975d2c
Source dataset
uspto-grants-1990_05
Patent number
US04929741

Reaction notes

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