Sodium hydride → HCID 18407068, compound

HRID 1016494Notes

Reaction equation

HRID 1016494 reaction equation
[Br:1][C:2]1[CH:14]=[CH:13][CH:12]=[CH:11][C:3]=1[CH2:4]P(=O)(OC)OC.[H-].[Na+].[C:17]([O:21][C:22]([N:24]1[CH2:29][CH2:28][C:27](=O)[CH2:26][CH2:25]1)=[O:23])([CH3:20])([CH3:19])[CH3:18]>C1COCC1>[C:17]([O:21][C:22]([N:24]1[CH2:29][CH2:28][C:27](=[CH:4][C:3]2[CH:11]=[CH:12][CH:13]=[CH:14][C:2]=2[Br:1])[CH2:26][CH2:25]1)=[O:23])([CH3:20])([CH3:18])[CH3:19]

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 735900tert-Butyl 4-oxopiperidine-1-carboxylateHCID 13729876HCID 13729876, compound

Product 1

HCID 18407068HCID 18407068, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Procedure

A solution of dimethyl 2-bromobenzylphosphonate (45.66 g, 148.9 mmol) in THF was added slowly to a mixture of NaH (7.14 g of a 60% mineral oil dispersion, 178.5 mmol) in THF (200 ml) and the mixture was stirred for 1 hr. A solution of 1-(tert-butoxycarbonyl)-4-piperidinone (29.67 g, 148.9 mmol) in THF was added dropwise and the mixture was heated to reflux for 1.5 hr. The mixture was cooled and quenched with brine. The mixture was diluted with ethyl acetate, washed with water, and dried with brine. The organic layer was concentrated in vacuo to an oil. The oil was dissolved in acetonitrile and extracted with hexane. The acetonitrile layer was concentrated in vacuo to give 1-(tert-butoxycarbonyl)-4-[(2-bromophenyl)methylene]piperidine (XI) as an oil that solidified upon standing (48.3 g, 97%).

Workup

  1. temperaturethe mixture was heated
  2. temperatureto reflux for 1.5 hr
  3. temperatureThe mixture was cooled
  4. customquenched with brine
  5. additionThe mixture was diluted with ethyl acetate
  6. washwashed with water
  7. dry with materialdried with brine
  8. concentrationThe organic layer was concentrated in vacuo to an oil
  9. dissolutionThe oil was dissolved in acetonitrile
  10. extractionextracted with hexane
  11. concentrationThe acetonitrile layer was concentrated in vacuo

Sources & evidence

ORD record
ord-2dda0f9865d64ef4a01ba4e73bef9567
Source dataset
uspto-grants-2002_11
Patent number
US06476051B2

Reaction notes

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