Potassium Hydroxide → 1-[4-(3-Ethynylphenoxy)phenyl]-2-phenylethane-1,2-dione

HRID 26028Notes

Reaction equation

HRID 26028 reaction equation
[C:1]([C:3]1[CH:4]=[C:5](C2C=C(S([O-])(=O)=O)C=CC=2C)[CH:6]=[CH:7][CH:8]=1)#[CH:2].[OH-:20].[K+].[N+]([C:25]1[CH:30]=[CH:29][C:28]([C:31]([C:33]([C:35]2[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=2)=[O:34])=[O:32])=[CH:27][CH:26]=1)([O-])=O.[OH-].[Na+]>CS(C)=O.CO>[C:1]([C:3]1[CH:4]=[C:5]([CH:6]=[CH:7][CH:8]=1)[O:20][C:25]1[CH:30]=[CH:29][C:28]([C:31]([C:33]([C:35]2[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=2)=[O:34])=[O:32])=[CH:27][CH:26]=1)#[CH:2]

Participants

7

Reactant 4

HCID 14797Potassium HydroxideHCID 14798Sodium HydroxideHCID 2838934-NitrobenzilHCID 227546443-Ethynylphenyl(p-toluenesulfonate)

Product 1

HCID 204033701-[4-(3-Ethynylphenoxy)phenyl]-2-phenylethane-1,2-dioneYield 65%

Reagents, catalysts & solvents 2

HCID 679Dimethyl SulfoxideSolvent2×HCID 887MethanolSolvent2×

Conditions

Temperature
90 °C

Procedure

To 100 ml of anhydrous methanol was added 20 g (0.073 mole) of 3-ethynylphenyl(p-toluenesulfonate) and 8.19 g (0.146 mole) of potassium hydroxide. The mixture was heated to reflux under a nitrogen atmosphere and maintained at reflux for 4 hours. A distillation apparatus was attached to the flask, and methanol was distilled from the flask until the residue approached dryness. Then, 400 ml of anhydrous benzene was added, and distillation was continued until 200 ml of benzene was removed. The reaction mixture was freeze dried under reduced pressure, leaving a dry, white powder. The white powder was dissolved in 150 ml of dimethylsulfoxide and transferred to an addition funnel under nitrogen. The solution was added over a 60 minute period to a solution of 4-nitrobenzil (18.6 g, 0.073 mole) in dimethylsulfoxide (300 ml) and stirred at 90° C. under nitrogen. When addition was completed, the reaction mixture was stirred overnight at 23° C. and poured into a solution of sodium hydroxide (50 g) in ice water (1 liter). Extraction with toluene (3 × 50 ml) followed by chromatography on silica gel with benzene as eluent gave 15.4 g (65% yield) of 4-(3-ethynylphenoxy)benzil as a yellow oil which solidified upon standing overnight at 23° C. into a pale yellow solid (m.p. 79°-81° C.).

Workup

  1. temperatureThe mixture was heated
  2. temperatureto reflux under a nitrogen atmosphere
  3. temperaturemaintained
  4. temperatureat reflux for 4 hours
  5. distillationwas distilled from the flask until the residue
  6. additionThen, 400 ml of anhydrous benzene was added
  7. distillationdistillation
  8. customwas removed
  9. customdried under reduced pressure
  10. customleaving a dry, white powder
  11. customtransferred to an addition funnel under nitrogen
  12. additionWhen addition
  13. stirringthe reaction mixture was stirred overnight at 23° C.
  14. extractionExtraction with toluene (3 × 50 ml)

Sources & evidence

ORD record
ord-33d3f27426b044beb6b2ebfb6477099e
Source dataset
uspto-grants-1979_04
Patent number
US04147868

Reaction notes

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