1,2-Dibromoethane → HCID 18670444, compound

HRID 1059333Notes

Reaction equation

HRID 1059333 reaction equation
C(NC(C)C)(C)C.C([Li])CCC.[CH2:13]([N:20]1[CH2:25][CH2:24][CH:23]([CH2:26][C:27]([O:29][CH2:30][CH3:31])=[O:28])[CH2:22][CH2:21]1)[C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1.[Br:32][CH2:33][CH2:34]Br>O1CCCC1.CN(P(N(C)C)(N(C)C)=O)C.CCCCCC.C(OCC)(=O)C.O>[CH2:13]([N:20]1[CH2:25][CH2:24][CH:23]([CH:26]([CH2:34][CH2:33][Br:32])[C:27]([O:29][CH2:30][CH3:31])=[O:28])[CH2:22][CH2:21]1)[C:14]1[CH:15]=[CH:16][CH:17]=[CH:18][CH:19]=1

Participants

10

Reactant 4

HCID 78391,2-DibromoethaneHCID 7912DiisopropylamineHCID 10400444HCID 10400444, compoundHCID 178418339Butyllithium

Product 1

HCID 18670444HCID 18670444, compound

Reagents, catalysts & solvents 5

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolventHCID 8857Ethyl AcetateSolventHCID 12679HexamethylphosphoramideSolvent

Conditions

Temperature
-78 °C

Procedure

13 ml of diisopropylamine was dissolved in a solvent mixture of tetrahydrofuran (140 ml) with HMPA (15 ml) in a nitrogen atmosphere and cooled to −78° C. Into the obtained solution was dropped 42 ml of a 2.5 M solution of n-butyllithium in hexane and the resulting mixture was stirred at 0° C. for 30 minutes. After cooling to −78° C. again, 15 ml of a solution of 5.8 g of ethyl (1-benzylpiperidin-4-yl)acetate in tetrahydrofuran was dropped thereinto. The reaction mixture was stirred at 0° C. for 1 hour. Then 1,2-dibromoethane was dropped thereinto at −78° C. again. The reaction mixture was stirred at 0° C. for 30 minutes and then brought back to room temperature. Next, it was distributed into water and ethyl acetate. The organic layer was extracted, washed with water and dried over magnesium sulfate. After distilling off the solvent under reduced pressure, the residue was purified by silica gel column chromatography (eluted with n-hexane/ethyl acetate) to thereby give 1.40 g of ethyl 2-(1-benzyl-4-piperidyl)-4-bromobutanoate as a colorless oily substance. A solution of 1.40 g of ethyl 2-(1-benzyl-4-piperidyl)-4-bromobutanoate in tetrahydrofuran (20 ml) was stirred at room temperature and 1.0 g of t-butoxypotassium was added thereto. The reaction mixture was distributed into water and ethyl acetate. The organic layer was extracted and washed with water. After distilling off the solvent under reduced pressure, the obtained residue was purified by silica gel column chromatography (eluted with n-hexane/ethyl acetate) to thereby give 800 mg of the title compound as a colorless oily substance.

Workup

  1. temperatureAfter cooling to −78° C. again
  2. stirringThe reaction mixture was stirred at 0° C. for 1 hour
  3. customat −78° C.
  4. stirringThe reaction mixture was stirred at 0° C. for 30 minutes
  5. custombrought back to room temperature
  6. extractionThe organic layer was extracted
  7. washwashed with water
  8. dry with materialdried over magnesium sulfate
  9. distillationAfter distilling off the solvent under reduced pressure
  10. customthe residue was purified by silica gel column chromatography (eluted with n-hexane/ethyl acetate)

Sources & evidence

ORD record
ord-454ab3aed338498cbdfe8dabeb531994
Source dataset
uspto-grants-2003_02
Patent number
US06518423B1

Reaction notes

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