Triethyl phosphonoacetate → tert-Butyl 4-(2-ethoxy-2-oxoethylidene)piperidine-1-carboxylate

HRID 458752Notes

Reaction equation

HRID 458752 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].C(OP([CH2:25][C:26]([O:28][CH2:29][CH3:30])=[O:27])(OCC)=O)C>O1CCCC1.C(OCC)(=O)C>[CH2:29]([O:28][C:26](=[O:27])[CH:25]=[C:13]1[CH2:14][CH2:15][N:10]([C:8]([O:7][C:3]([CH3:6])([CH3:5])[CH3:4])=[O:9])[CH2:11][CH2:12]1)[CH3:30]

Participants

6

Reactant 3

HCID 13345Triethyl phosphonoacetateHCID 24758Sodium hydrideHCID 735900tert-Butyl 4-oxopiperidine-1-carboxylate

Product 1

HCID 10333298tert-Butyl 4-(2-ethoxy-2-oxoethylidene)piperidine-1-carboxylate

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

To a solution of 9.1 g of 60% oily sodium hydride in 200 ml of tetrahydrofuran, 38.0 ml of ethyl diethylphosphonoacetate was added dropwise under cooling with ice, stirred for 20 minutes, and thereafter a solution of 31.4 g of 1-t-butoxycarbonyl-4-piperidone in 500 ml of tetrahydrofuran was added dropwise, followed by 40 minutes' stirring at the same temperature. The reaction liquid was diluted with ethyl acetate, washed successively with aqueous ammonium chloride solution, water and saturated brine, and dried over anhydrous sodium sulfate. Distilling the solvent off under reduced pressure, the residue was recrystallized from methanol to provide 33.5 g of the title compound.

Workup

  1. temperatureunder cooling with ice
  2. waitfollowed by 40 minutes
  3. stirring' stirring at the same temperature
  4. customThe reaction liquid
  5. washwashed successively with aqueous ammonium chloride solution, water and saturated brine
  6. dry with materialdried over anhydrous sodium sulfate
  7. distillationDistilling the solvent off under reduced pressure
  8. customthe residue was recrystallized from methanol

Sources & evidence

ORD record
ord-7211eb55d2164bc2bb7035c382f2d558
Source dataset
uspto-grants-2007_03
Patent number
US07192969B2

Reaction notes

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