Furfuryl Alcohol → 6-Acetoxy-2H-pyran-3(6H)-one

HRID 2170524Notes

Reaction equation

HRID 2170524 reaction equation
C(=O)([O-])O.[Na+].[C:6]([O-:9])(=[O:8])[CH3:7].[Na+].BrN1C(=O)CCC1=O.[CH2:19]([OH:25])[C:20]1[O:24][CH:23]=[CH:22][CH:21]=1.C(OC(=O)C)(=O)C.[OH-].[Na+]>O.C1COCC1.CN(C1C=CN=CC=1)C>[C:6]([O:9][CH:23]1[CH:22]=[CH:21][C:19](=[O:25])[CH2:20][O:24]1)(=[O:8])[CH3:7]

Participants

10

Reactant 6

HCID 7361Furfuryl Alcohol2×HCID 7918Acetic AnhydrideHCID 14798Sodium HydroxideHCID 67184N-bromobutanimideHCID 516892Sodium BicarbonateHCID 517045Sodium Acetate

Product 1

HCID 111162906-Acetoxy-2H-pyran-3(6H)-oneYield 66.1%

Reagents, catalysts & solvents 3

HCID 142844-(Dimethylamino)pyridineCatalystHCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-15 °C

Procedure

2055 g of sodium hydrogen carbonate and 1004 g of sodium acetate were dissolved in a mixed solvent of 1.8 L of water and 15 L of THF. The resultant was cooled to −15° C., and 1.2 L of THF solution containing 2257 g of N-bromosuccinimide was added while maintaining the temperature at 0° C. or lower. Furthermore, 1200 g of furfuryl alcohol (Compound 1) was added while maintaining the temperature at 0° C. or lower, and agitated at the same temperature for 10 minutes. After confirming the end of the reaction by thin-layer chromatography, 299 g of DMAP and 2498 g of acetic anhydride were added while maintaining the temperature at 0° C. or lower. The reaction solution was heated to 30° C. and agitated at that temperature for 3.5 hours. After confirming the end of the reaction by thin-layer chromatography, the solution was cooled to 5° C., and added with 9.5 L of 2 N aqueous sodium hydroxide solution to prepare a solution of pH 6.5. This reaction solution was extracted with ethyl acetate and washed with a saturated sodium bicarbonate solution to obtain the organic layer. The solvent was distilled away under reduced pressure to obtain 1263 g of a crude product (±) 4 as a clear brown oily product (crude yield: 71.1%).

Workup

  1. additionwas added
  2. temperaturewhile maintaining the temperature at 0° C.
  3. temperaturewhile maintaining the temperature at 0° C.
  4. additionwere added
  5. temperaturewhile maintaining the temperature at 0° C.
  6. temperatureThe reaction solution was heated to 30° C.
  7. stirringagitated at that temperature for 3.5 hours
  8. customthe end of the reaction by thin-layer chromatography
  9. temperaturethe solution was cooled to 5° C.
  10. customto prepare a solution of pH 6.5
  11. extractionThis reaction solution was extracted with ethyl acetate
  12. washwashed with a saturated sodium bicarbonate solution
  13. customto obtain the organic layer
  14. distillationThe solvent was distilled away under reduced pressure

Sources & evidence

ORD record
ord-dc5572c8e9664edea90d8e548dc86021
Source dataset
uspto-grants-2015_06
Patent number
US09051288B2

Reaction notes

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