Dimethyl Carbonate → Methyl 4-oxooxane-3-carboxylate

HRID 1752230Notes

Reaction equation

HRID 1752230 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-5971f71807cf491ab92204c80634b5d0
Source dataset
uspto-grants-2015_10
Patent number
US09163003B2

Reaction notes

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