Methyl propiolate → HCID 23050481, compound

HRID 1651809Notes

Reaction equation

HRID 1651809 reaction equation
[C:1]([O:5][CH3:6])(=[O:4])[C:2]#[CH:3].C([Li])CCC.[F:12][C:13]1[CH:20]=[CH:19][C:16]([CH:17]=[O:18])=[CH:15][CH:14]=1.[Cl-].[NH4+]>O1CCCC1>[F:12][C:13]1[CH:20]=[CH:19][C:16]([CH:17]([OH:18])[C:3]#[C:2][C:1]([O:5][CH3:6])=[O:4])=[CH:15][CH:14]=1

Participants

6

Reactant 4

HCID 13536Methyl propiolateHCID 25517Ammonium ChlorideHCID 680234-FluorobenzaldehydeHCID 178418339Butyllithium

Product 1

HCID 23050481HCID 23050481, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A solution of 7.5 ml (90 mmol) of methyl propiolate in 80 ml of tetrahydrofuran was treated at -78° under argon 10 with 56.3 ml of n-butyllithium (1.6M in hexane). The mixture was stirred at -78° for 10 minutes and then a solution of 8.4 ml (80 mmol) of 4-fluorobenzaldehyde in 80 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 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 800 g of silica gel (elution agent methylene chloride/ethyl acetate 9:1). There was obtained methyl 4-(4-fluorophenyl)-4-hydroxy-2-butynoate as a yellow 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 800 g of silica gel (elution agent methylene chloride/ethyl acetate 9:1)

Sources & evidence

ORD record
ord-a66b87d5ec9548e3b412df1c21e3e593
Source dataset
uspto-grants-1990_05
Patent number
US04929741

Reaction notes

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