Acetonitrile → 1,3-Bis(benzyloxy)propan-2-one

HRID 1006406Notes

Reaction equation

HRID 1006406 reaction equation
[CH2:1]([O:8][CH2:9][CH:10]([OH:20])[CH2:11][O:12][CH2:13][C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C(#N)C.C(=O)(O)[O-].[Na+].Cl[O-].[Na+]>C(OC)(C)(C)C>[CH2:1]([O:8][CH2:9][C:10](=[O:20])[CH2:11][O:12][CH2:13][C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

6

Reactant 4

HCID 6342AcetonitrileHCID 2476141,3-Bis(benzyloxy)propan-2-olHCID 516892Sodium BicarbonateHCID 23665760Sodium Hypochlorite2×

Product 1

HCID 113915821,3-Bis(benzyloxy)propan-2-oneYield 93%

Reagents, catalysts & solvents 1

HCID 15413tert-Butyl methyl etherSolvent

Conditions

Temperature
1.100000023841858 °C

Procedure

1,3-dibenzyloxy-2-propanol(100.0 g, 367 mmol), acetonitrile (1352 mL) and 2,2,6,6-tetramethyl-1-piperidinyloxy free radical (5.74 g, 36.7 mmol) were placed in a 5,000-mL four-necked flask equipped with a mechanical stirrer and a thermometer under a nitrogen stream, and the mixture was stirred for 5 minutes. Then, 3% aqueous sodium bicarbonate solution (1,028 g, 367 mmol) was added and the mixture was cooled to 1.1° C. using an ice bath. 11.9% aqueous sodium hypochlorite solution (when 10% aqueous sodium hypochlorite solution on the market was titrated, the accurate concentration was 11.9%) (276 g, 441 mmol) was added to the mixture over a period of more than 2 hours while keeping the temperature of the mixture at 5° C. or less (the reaction was a little exothermic), and the mixture was stirred at from 0.5° C. to 2.0° C. for 1 hour. Methyl t-butyl ether (2,700 mL) was added to the reaction mixture, the mixture was stirred for 20 minutes while keeping the temperature at 10° C. or less and allowed to stand for 10 minutes, and the resulting two layers were separated (the water layer weighed 1, 289 g and its pH was 8). The obtained organic layer was washed with 10% aqueous sodium sulfite solution (330 g), 5% saline (200 g) and 20% saline (200 g) in this order. The resulting solution (3,130 g) was analyzed by high performance liquid chromatography and as a result 91.8 g (yield 93%) of the captioned 1,3-dibenzyloxypropanone was obtained.

Workup

  1. customequipped with a mechanical stirrer
  2. additionthe accurate concentration was 11.9%) (276 g, 441 mmol) was added to the mixture over a period of more than 2 hours
  3. customat 5° C. or less
  4. stirringwas stirred at from 0.5° C. to 2.0° C. for 1 hour
  5. stirringthe mixture was stirred for 20 minutes
  6. customat 10° C. or less
  7. waitto stand for 10 minutes
  8. customthe resulting two layers were separated (the water layer
  9. washThe obtained organic layer was washed with 10% aqueous sodium sulfite solution (330 g), 5% saline (200 g) and 20% saline (200 g) in this order

Sources & evidence

ORD record
ord-c154f1e145b3473382e71500a9453c47
Source dataset
uspto-grants-2004_09
Patent number
US06790836B2

Reaction notes

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