Acetophenone → HCID 18690517, compound

HRID 1585271Notes

Reaction equation

HRID 1585271 reaction equation
[H-].[Na+].[C:3]([O:12]C)(=O)[CH2:4][CH2:5][CH2:6][C:7]([CH3:10])([CH3:9])[CH3:8].[C:14]([C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1)(=[O:16])[CH3:15]>C1(C)C(C)=CC=CC=1>[C:17]1([C:14](=[O:16])[CH2:15][C:3]([CH2:4][CH2:5][CH2:6][C:7]([CH3:8])([CH3:9])[CH3:10])=[O:12])[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1

Participants

5

Reactant 3

HCID 7410AcetophenoneHCID 24758Sodium hydrideHCID 18690527HCID 18690527, compound

Product 1

HCID 18690517HCID 18690517, compoundYield 53%

Reagents, catalysts & solvents 1

HCID 7237O-XyleneSolvent2×

Conditions

Temperature
135 °C

Procedure

A 500 mL 4 neck round bottom flask equipped with mechanical stirring, a nitrogen inlet, a thermometer, a condenser, and an addition funnel was charged with 60% sodium hydride in mineral oil (20.5 g, 0.51 mol), methyl neo-octanoate (92.3 g, 0.58 mol), and xylene (42.8 g). The mixture was heated to reflux (135° C.), and then a solution of acetophenone (32.4 g, 0.27 mol) in xylene (19.1 g) was added over 1.25 h. The mixture was kept at reflux for an additional 1 h. After cooling to room temperature, the reaction was quenched by the careful addition of methanol (20 mL), and then acidified with 150 g/L sulfuric acid (180 mL). After separation of layers, the organic phase was washed with water (2×100 mL) and brine (100 mL). After drying by passing through anhydrous sodium sulfate, the solution was concentrated in vacuo at 70° C. down to 12 mbar to yield an orange liquid containing product in a crude yield of 63%. Vacuum distillation (200 mtorr) through a 15 cm Vigreux column yielded the product in the heart cut: 1-phenyl-3-neoheptyl-1,3-propanedione (37.2 g, 96% pure, 0.14 mol; 53% yield; bp: 94-135° C.). Dypnone was undetectable in the product.

Workup

  1. temperatureThe mixture was heated
  2. temperatureat reflux for an additional 1 h
  3. temperatureAfter cooling to room temperature
  4. customthe reaction was quenched by the careful addition of methanol (20 mL)
  5. customAfter separation of layers
  6. washthe organic phase was washed with water (2×100 mL) and brine (100 mL)
  7. customAfter drying
  8. concentrationthe solution was concentrated in vacuo at 70° C. down to 12 mbar
  9. customto yield an orange liquid
  10. additioncontaining product in a crude yield of 63%
  11. distillationVacuum distillation (200 mtorr) through a 15 cm Vigreux column
  12. customyielded the product in the heart cut

Sources & evidence

ORD record
ord-7cbad38f0315465f8c2205b41a4f7fcf
Source dataset
uspto-grants-1999_08
Patent number
US05936129

Reaction notes

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