Hydrochloric Acid → Tert-butyl 4-(2-methoxy-2-oxoethylidene)piperidine-1-carboxylate

HRID 1061022Notes

Reaction equation

HRID 1061022 reaction equation
[H-].[Na+].[C:3]([O:7][C:8]([N:10]1[CH2:15][CH2:14][C:13](=O)[CH2:12][CH2:11]1)=[O:9])([CH3:6])([CH3:5])[CH3:4].Cl.COP([CH2:24][C:25]([O:27][CH3:28])=[O:26])(OC)=O>O1CCCC1.C(OCC)(=O)C>[C:3]([O:7][C:8]([N:10]1[CH2:15][CH2:14][C:13](=[CH:24][C:25]([O:27][CH3:28])=[O:26])[CH2:12][CH2:11]1)=[O:9])([CH3:6])([CH3:5])[CH3:4]

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 24758Sodium hydrideHCID 80029Trimethyl phosphonoacetateHCID 735900tert-Butyl 4-oxopiperidine-1-carboxylate

Product 1

HCID 10377658Tert-butyl 4-(2-methoxy-2-oxoethylidene)piperidine-1-carboxylate

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

In tetrahydrofuran (40 ml), methyl dimethylphosphono-acetate (1.8 ml) was dissolved. To the resulting solution, 60% oily sodium hydride (450 mg) was added under ice cooling, followed by stirring under the same condition. After the addition of a solution of 1-(tert-butoxycarbonyl)-4-piperidone (2.05 g) in tetrahydrofuran (tetrahydrofuran: 10 ml) and stirring at room temperature for 30 minutes, the reaction mixture was diluted with ethyl acetate. To the diluted solution, 2N hydrochloric acid was added. The organic layer was separated, washed with a saturated aqueous solution of sodium bicarbonate and saturated aqueous saline, and dried over anhydrous sodium sulfate. The solvent was then distilled off under reduced pressure. The residue was purified by chromatography on a silica gel column (hexane:ethyl acetate=6:1), whereby the title compound (2.35 g, 92%) was obtained.

Workup

  1. stirringstirring at room temperature for 30 minutes
  2. customThe organic layer was separated
  3. washwashed with a saturated aqueous solution of sodium bicarbonate and saturated aqueous saline
  4. dry with materialdried over anhydrous sodium sulfate
  5. distillationThe solvent was then distilled off under reduced pressure
  6. customThe residue was purified by chromatography on a silica gel column (hexane:ethyl acetate=6:1), whereby the title compound (2.35 g, 92%)
  7. customwas obtained

Sources & evidence

ORD record
ord-cac244da30d441f2bf786049e317a075
Source dataset
uspto-grants-2003_02
Patent number
US06525042B1

Reaction notes

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