Water → tert-Butyl 4-(2-ethoxy-2-oxoethylidene)piperidine-1-carboxylate
Reaction equation
O=[C:2]1[CH2:7][CH2:6][N:5]([C:8]([O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[O:9])[CH2:4][CH2:3]1.[H-].[Na+].[OH2:17].[CH2:18]1[CH2:22][O:21][CH2:20][CH2:19]1>>[CH2:20]([O:21][C:22](=[O:17])[CH:18]=[C:2]1[CH2:7][CH2:6][N:5]([C:8]([O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[O:9])[CH2:4][CH2:3]1)[CH3:19]Participants
Procedure
A solution of tert-butyl 4-oxopiperidine-1-carboxylate (10.0 g, 50.25 mmol, 1 eq) in THF (50 ml) was added at 0° C. to a suspension of NaH (1.56 g, 65.32 mmol, 1.3 eq) in THF (50 ml), and stirring was carried out for 30 min. Triethyl phosphoroacetate (12.96 ml, 65.32 mmol, 1.3 eq) in THF (50 ml) was added dropwise, and stirring was carried out for 2 h at RT. The reaction mixture was hydrolyzed with water (5 ml) and concentrated. The residue was taken up in water (150 ml) and extracted with ethyl acetate (2×300 ml). The combined organic phases were washed with sat. NaCl solution (200 ml), dried over sodium sulfate and concentrated under reduced pressure. The crude substance was purified by column chromatography (silica gel, 3% ethyl acetate in hexane) (white solid). Yield: 78% (10.5 g, 39.03 mmol).
Workup
- stirringstirring
- waitwas carried out for 2 h at RT
- concentrationconcentrated
- extractionextracted with ethyl acetate (2×300 ml)
- washThe combined organic phases were washed with sat. NaCl solution (200 ml)
- dry with materialdried over sodium sulfate
- concentrationconcentrated under reduced pressure
- customThe crude substance was purified by column chromatography (silica gel, 3% ethyl acetate in hexane) (white solid)
Sources & evidence
- ORD record
- ord-890b4d00714445caaa8887c66973b64e
- Source dataset
- uspto-grants-2014_03
- Patent number
- US08680159B2
Reaction notes
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