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

HRID 1039976

반응식

HRID 1039976 반응식
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]

참가 물질

5

반응물 3

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

생성물 1

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

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매2회

실험 절차

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).

후처리

  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)

출처 및 근거

ORD 기록
ord-f140cb066a19433bb2889867e24e23f1
출처 데이터셋
uspto-grants-2013_10
특허 번호
US08551984B2

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