4-Hydroxybenzaldehyde → HCID 23050488, compound

HRID 1651817Notes

Reaction equation

HRID 1651817 reaction equation
[C:1]([O:5][CH3:6])(=[O:4])[C:2]#[CH:3].C([Li])CCC.[OH:12][C:13]1[CH:20]=[CH:19][C:16]([CH:17]=[O:18])=[CH:15][CH:14]=1.[Cl-].[NH4+]>O1CCCC1>[OH:18][CH:17]([C:16]1[CH:19]=[CH:20][C:13]([OH:12])=[CH:14][CH:15]=1)[C:3]#[C:2][C:1]([O:5][CH3:6])=[O:4]

Participants

6

Reactant 4

HCID 1264-HydroxybenzaldehydeHCID 13536Methyl propiolateHCID 25517Ammonium ChlorideHCID 178418339Butyllithium

Product 1

HCID 23050488HCID 23050488, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A solution of 12.5 ml (0.15 mol) of methyl propiolate in 150 ml of tetrahydrofuran was treated at -78° under argon with 100 ml of n-butyllithium (1.6M in hexane). The mixture was stirred at -78° for 10 minutes and then a solution of 9.8 g (80 mmol) of 4-hydroxybenzaldehyde in 50 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 200 ml of saturated ammonium chloride solution. The aqueous phase was extracted twice with ether. The combined organic phases were dried in sequence with saturated 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-hydroxy-4-(4-hydroxyphenyl)-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. dry with materialThe combined organic phases were dried in sequence with saturated sodium sulphate
  5. concentrationconcentrated The residue
  6. customwas purified by flash chromatography on 1000 g of silica gel (elution agent methylene chloride/ethyl acetate 9:1)

Sources & evidence

ORD record
ord-99c3656f171447cf957ab1c674b44420
Source dataset
uspto-grants-1990_05
Patent number
US04929741

Reaction notes

Loading…