4-Chlorobenzaldehyde → HCID 11535916, compound

HRID 1651811Notes

Reaction equation

HRID 1651811 reaction equation
[C:1]([O:5][CH3:6])(=[O:4])[C:2]#[CH:3].C([Li])CCC.[Cl:12][C:13]1[CH:20]=[CH:19][C:16]([CH:17]=[O:18])=[CH:15][CH:14]=1.[Cl-].[NH4+]>O1CCCC1>[Cl: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 77264-ChlorobenzaldehydeHCID 13536Methyl propiolateHCID 25517Ammonium ChlorideHCID 178418339Butyllithium

Product 1

HCID 11535916HCID 11535916, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A solution of 8.36 ml (0.1 mol) of methyl propiolate in 100 ml of tetrahydrofuran was treated at -78° under argon with 68.8 ml of n-butyllithium (1.6M in hexane). The mixture was stirred at -78° for 10 minutes and then a solution of 14.06 g (0.1 mol) of 4-chlorobenzaldehyde in 100 ml of tetrahydrofuran was added within 40 minutes. The reaction mixture is stirred at -78° for a further 20 minutes, then brought to room temperature and treated with 100 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/ethyl acetate 9:1). There was obtained methyl 4-(4-chlorophenyl)-4-hydroxy-2-butynoate as a red oil.

Workup

  1. stirringThe reaction mixture is 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 1000 g of silica gel (elution agent methylene chloride/ethyl acetate 9:1)

Sources & evidence

ORD record
ord-48fc1089bd3146c78d76c46fa5822041
Source dataset
uspto-grants-1990_05
Patent number
US04929741

Reaction notes

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