4-Methylbenzaldehyde → HCID 23050515, compound

HRID 1651812Notes

Reaction equation

HRID 1651812 reaction equation
[C:1]([O:5][CH3:6])(=[O:4])[C:2]#[CH:3].C([Li])CCC.[CH3:12][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]([CH3:12])=[CH:14][CH:15]=1)[C:3]#[C:2][C:1]([O:5][CH3:6])=[O:4]

Participants

6

Reactant 4

HCID 77254-MethylbenzaldehydeHCID 13536Methyl propiolateHCID 25517Ammonium ChlorideHCID 178418339Butyllithium

Product 1

HCID 23050515HCID 23050515, 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 68.8 ml of n-butyllithium (1.6M in hexane). The mixture was stirred at -78° for 10 minutes and then a solution of 11.8 ml (0.1 mol) of 4-methylbenzaldehyde 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 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-hydroxy-4-(4-methylphenyl)-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. extractionwas 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-72388fbc065f43bc942214171b9b6005
Source dataset
uspto-grants-1990_05
Patent number
US04929741

Reaction notes

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