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

HRID 551417Notes

Reaction equation

HRID 551417 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.[Br-].[K+].[O-]Cl.[Na+].C([O-])(O)=O.[Na+]>ClCCl.O.CC1(C)N([O])C(C)(C)CCC1>[C:14]1([CH2:13][O:12][CH2:11][C:10](=[O:20])[CH2:9][O:8][CH2:1][C:2]2[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=2)[CH:15]=[CH:16][CH:17]=[CH:18][CH:19]=1

Participants

8

Reactant 4

HCID 2476141,3-Bis(benzyloxy)propan-2-olHCID 253877Potassium BromideHCID 516892Sodium BicarbonateHCID 23665760Sodium Hypochlorite2×

Product 1

HCID 113915821,3-Bis(benzyloxy)propan-2-oneYield 179.5%

Reagents, catalysts & solvents 3

HCID 2724126TempoCatalystHCID 962WaterSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
-10 °C

Procedure

A solution of 1,3-dibenzyloxy-2-propanol (500 g, 1.84 mol 1.0 eq.), TEMPO (5.5 g, 0.034 mol) in dichloromethane (1.25 L) was placed in a 10 L flange flask fitted with overhead stirrer. A solution of potassium bromide (48 g, 0.40 mol) in water (185 ml) was added and the reaction stirred and cooled to −10° C. A 14% aqueous NaOCl solution was diluted to 1M (2145 g diluted to 4050 ml). The pH of this solution was then adjusted to 9.5 by dissolving NaHCO3 (80 g) immediately before use. This NaOCl solution was added over 1 hour, keeping the temperature of the reaction mixture between 10-15° C. The mixture was the stirred for 60 minutes. The orange coloured organic phase was separated and the aqueous layer was extracted with dichloromethane (5.0 L, 2.0 L). The combined organics were washed with 10% aq. HCl (10.75 L) containing potassium iodide (143 g), 10% aq. Na2S2O5 (5.0 L) and water (5.0 L). The organics were dried over MgSO4 and concentrated under reduced pressure to give the crude title compound (893 g, 90%). This compound was taken through to the next step without further purification.

Workup

  1. customfitted with overhead stirrer
  2. custombetween 10-15° C
  3. stirringstirred for 60 minutes
  4. customwas separated
  5. extractionthe aqueous layer was extracted with dichloromethane (5.0 L, 2.0 L)
  6. washThe combined organics were washed with 10% aq. HCl (10.75 L)
  7. additioncontaining potassium iodide (143 g), 10% aq. Na2S2O5 (5.0 L) and water (5.0 L)
  8. dry with materialThe organics were dried over MgSO4
  9. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-e5c922b6ab5141878cd18d7053092498
Source dataset
uspto-grants-2011_05
Patent number
US07947727B2

Reaction notes

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