Dimethyl Carbonate → Methyl 4-oxooxane-3-carboxylate

HRID 588706Notes

Reaction equation

HRID 588706 reaction equation
[O:1]1[CH2:6][CH2:5][C:4](=[O:7])[CH2:3][CH2:2]1.[CH3:8][O:9][C:10](=O)[O:11]C.CC(C)([O-])C.[K+]>>[CH3:8][O:9][C:10]([CH:3]1[C:4](=[O:7])[CH2:5][CH2:6][O:1][CH2:2]1)=[O:11]

Participants

4

Reactant 3

HCID 12021Dimethyl CarbonateHCID 121599Tetrahydro-4H-pyran-4-one2×HCID 23665647Potassium tert-butoxide

Product 1

HCID 14666555Methyl 4-oxooxane-3-carboxylateYield 26.5%

Procedure

To a solution of tetrahydro-pyran-4-one (1.3 kg, 12.98 mol) and carbonic acid dimethyl ester (11.69 kg, 129.8 mol) was added solid potassium tert-butoxide (1.89 kg, 16.08 mol) in portions at −10° C. over 2 h under nitrogen protection. The suspension was stirred at room temperature 10 h after the addition. LCMS (215 nm) indicated that tetrahydro-pyran-4-one had been completely consumed. The reaction was acidified by HCl (2 N) to pH 6˜7 and then the phases were separated. The organic phase was washed with water (3 L×2) and the combined aqueous phases were extracted with MTBE (2.5 L×2). The combined organic phase was concentrated under reduced pressure at 25° C. to remove most of MTBE. The residue was distilled out by oil pump (˜200 Pa) at 74° C. to give the title compound as colorless oil (545 g, 26.3%). CHN analysis: calculated (results). C, 53.16; (53.10), H, 6.37; (6.245), N, 0.00; (0.00).

Workup

  1. additionafter the addition
  2. customhad been completely consumed
  3. customthe phases were separated
  4. washThe organic phase was washed with water (3 L×2)
  5. extractionthe combined aqueous phases were extracted with MTBE (2.5 L×2)
  6. concentrationThe combined organic phase was concentrated under reduced pressure at 25° C.
  7. customto remove most of MTBE
  8. distillationThe residue was distilled out by oil pump (˜200 Pa) at 74° C.

Sources & evidence

ORD record
ord-b6ce49adb8b5412791b4e1827b788180
Source dataset
uspto-grants-2016_01
Patent number
US09227982B2

Reaction notes

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