Dimethyl Carbonate → Methyl 4-oxooxane-3-carboxylate

HRID 713379ノート

反応式

HRID 713379 の反応式
[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]

参加物

4

反応物 3

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

生成物 1

HCID 14666555Methyl 4-oxooxane-3-carboxylate収率 26.5%

実験手順

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).

後処理

  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.

出典と根拠

ORDレコード
ord-c7949e44dc8049629dbfdf2249bcfd03
出典データセット
uspto-grants-2015_11
特許番号
US09181266B2

反応ノート

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