Dimethyl (2-oxopropyl)phosphonate → methyl(3E)-2,2-dimethyl-5-oxohex-3-enoate

HRID 1039976

反応式

HRID 1039976 の反応式
COP([CH2:7][C:8](=[O:10])[CH3:9])(=O)OC.CC(C)([O-])C.[K+].[CH3:17][C:18]([CH3:25])([CH:23]=O)[C:19]([O:21][CH3:22])=[O:20]>O1CCCC1>[CH3:17][C:18]([CH3:25])(/[CH:23]=[CH:7]/[C:8](=[O:10])[CH3:9])[C:19]([O:21][CH3:22])=[O:20]

参加物

5

反応物 3

HCID 77872Dimethyl (2-oxopropyl)phosphonateHCID 11137194Methyl 2,2-dimethyl-3-oxopropanoateHCID 23665647Potassium tert-butoxide

生成物 1

HCID 86658242methyl(3E)-2,2-dimethyl-5-oxohex-3-enoate収率 47%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒2 回

実験手順

To a solution of dimethyl(2-oxopropyl)phosphonate (4.09 mL, 30 mmol) in tetrahydrofuran (200 mL) at 0° C. was added potassium tert-butoxide (3.22 g, 28.7 mmol). After 15 minutes, the reaction flask was moved to a 20° C. water bath and then a solution of methyl 2,2-dimethyl-3-oxopropanoate (3.39 g, 26 mmol) in tetrahydrofuran (10 mL) was added. After 20 hours, the opaque reaction mixture was partitioned between diethyl ether (100 mL) and water (100 mL). The layers were separated and the aqueous layer was extracted with diethyl ether (1×100 mL, 1×50 mL). The combined organic layers were washed with saturated aqueous sodium bicarbonate solution and brine, dried over sodium sulfate, filtered, and concentrated. The residue was purified by silica gel flash column chromatography (0-4% methanol/dichloromethane gradient) to afford methyl(3E)-2,2-dimethyl-5-oxohex-3-enoate (2.21 g, 12.21 mmol, 47% yield) as a light yellow oil. 1H NMR (500 MHz, CDCl3) δ 6.95 (d, J=16.3, 1H), 6.09 (d, J=16.3, 1H), 3.71 (s, 3H), 2.29 (s, 3H), 1.37 (d, J=2.3, 6H).

後処理

  1. customwas moved to a 20° C.
  2. waitAfter 20 hours
  3. customthe opaque reaction mixture
  4. customwas partitioned between diethyl ether (100 mL) and water (100 mL)
  5. customThe layers were separated
  6. extractionthe aqueous layer was extracted with diethyl ether (1×100 mL, 1×50 mL)
  7. washThe combined organic layers were washed with saturated aqueous sodium bicarbonate solution and brine
  8. dry with materialdried over sodium sulfate
  9. filtrationfiltered
  10. concentrationconcentrated
  11. customThe residue was purified by silica gel flash column chromatography (0-4% methanol/dichloromethane gradient)

出典と根拠

ORDレコード
ord-f140cb066a19433bb2889867e24e23f1
出典データセット
uspto-grants-2013_10
特許番号
US08551984B2

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