p-Bromochlorobenzene → HCID 69479698, compound

HRID 856089Notes

Reaction equation

HRID 856089 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([Cl:8])=[CH:4][CH:3]=1.[NH:9]1[CH2:14][CH2:13][CH:12]([N:15]([CH3:23])[C:16](=[O:22])[O:17][C:18]([CH3:21])([CH3:20])[CH3:19])[CH2:11][CH2:10]1.CC(C)([O-])C.[Na+].C(OCC)(=O)C>C1(C)C=CC=CC=1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1C=CC(P(C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.O>[Cl:8][C:5]1[CH:6]=[CH:7][C:2]([N:9]2[CH2:10][CH2:11][CH:12]([N:15]([CH3:23])[C:16](=[O:22])[O:17][C:18]([CH3:19])([CH3:20])[CH3:21])[CH2:13][CH2:14]2)=[CH:3][CH:4]=1

Participants

9

Reactant 4

HCID 7806p-BromochlorobenzeneHCID 8857Ethyl AcetateHCID 27568064-N-Boc-4-N-Methyl-aminopiperidineHCID 23676156Sodium t-butoxide

Product 1

HCID 69479698HCID 69479698, compoundYield 134%

Reagents, catalysts & solvents 4

HCID 167845palladium(II) acetateCatalystHCID 634876Binap, (A+-)-CatalystHCID 962WaterSolventHCID 1140TolueneSolvent

Procedure

A mixture of p-bromochlorobenzene (3.13 g, 16.3 mmol), tert-butyl (piperidin-4-yl)-N-methylcarbamate (3.5 g, 10.8 mmol), palladium acetate (73 mg, 0.33 mmol), (S)-(−)-BINAP (305 mg, 0.49 mmol) and sodium tert-butoxide (2.2 g, 22.9 mmol) in toluene (30 ml) was refluxed under a nitrogen atmosphere for 3 hours. Ethyl acetate and water were added to the reaction mixture, the mixture was stirred for a while. The insoluble substances were removed by filtration through Celite, and the filtrate was extracted with ethyl acetate. The extract was washed with brine, dried over magnesium sulfate, and then filtered. The filtrate was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (methylene chloride/ethyl acetate=10/1) to afford tert-butyl N-[1-(4-chlorophenyl)piperidin-4-yl]-N-methylcarbamate (4.7 g, yield 89%) as a yellow powder.

Workup

  1. temperaturewas refluxed under a nitrogen atmosphere for 3 hours
  2. customThe insoluble substances were removed by filtration through Celite
  3. extractionthe filtrate was extracted with ethyl acetate
  4. washThe extract was washed with brine
  5. dry with materialdried over magnesium sulfate
  6. filtrationfiltered
  7. concentrationThe filtrate was concentrated under reduced pressure
  8. customthe residue was purified by silica gel column chromatography (methylene chloride/ethyl acetate=10/1)

Sources & evidence

ORD record
ord-36264ef40ae2453896476c14795d283e
Source dataset
uspto-grants-2007_08
Patent number
US07262212B2

Reaction notes

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