Benzyl 4-bromophenylcarbamate → HCID 54574831, compound

HRID 1740136Notes

Reaction equation

HRID 1740136 reaction equation
[C:1]([NH:11][C:12]1[CH:17]=[CH:16][C:15](Br)=[CH:14][CH:13]=1)([O:3][CH2:4][C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1)=[O:2].C([Li])CCC.[C:24]([N:34]1[CH2:39][CH2:38][C:37](=[O:40])[CH2:36][CH2:35]1)([O:26][CH2:27][C:28]1[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1)=[O:25]>O1CCCC1>[C:28]1([CH2:27][O:26][C:24]([N:34]2[CH2:35][CH2:36][C:37]([OH:40])([C:15]3[CH:16]=[CH:17][C:12]([NH:11][C:1]([O:3][CH2:4][C:5]4[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=4)=[O:2])=[CH:13][CH:14]=3)[CH2:38][CH2:39]2)=[O:25])[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1

Participants

5

Reactant 3

HCID 561232Benzyl 4-bromophenylcarbamateHCID 643496Benzyl 4-oxopiperidine-1-carboxylateHCID 178418339Butyllithium

Product 1

HCID 54574831HCID 54574831, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

To a solution of N-(carbobenzyloxy)-4-bromaniline (5.00 g) in dry tetrahydrofuran (80 mL) at -78° C. under N2 is added n-butyllithium (21.4 mL, 1.6 M in hexanes) dropwise over five minutes. The resulting yellow solution is stirred at -78° C. for 30 minutes and is then treated with a solution of N-(carbobenzyloxy)-4-piperidone (3.99 g) in dry tetrahydrofuran (17 mL). The reaction mixture is stirred for three hours, during which the reaction temperature is allowed to rise to 0° C. and is quenched with saturated aqueous ammonium chloride (30 mL). The mixture is then diluted with water (100 mL), the layers are separated, the aqueous phase is extracted with diethyl ether, and the combined organic phase is washed with saline (50 mL), dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue is chromato-graphed on silica gel (230-400 mesh, 350 g), eluting with ethyl acetate/hexane (25/75), and those fractions with an Rf =0.38 by TLC (ethyl acetate/hexane, 50/50) are pooled and concentrated under reduced pressure to give the title compound, mp 156° C.-158° C.

Workup

  1. stirringThe reaction mixture is stirred for three hours, during which the reaction temperature
  2. customto rise to 0° C.
  3. customis quenched with saturated aqueous ammonium chloride (30 mL)
  4. additionThe mixture is then diluted with water (100 mL)
  5. customthe layers are separated
  6. extractionthe aqueous phase is extracted with diethyl ether
  7. washthe combined organic phase is washed with saline (50 mL)
  8. dry with materialdried over anhydrous sodium sulfate
  9. concentrationconcentrated under reduced pressure
  10. washeluting with ethyl acetate/hexane (25/75)
  11. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-152d673f84a04eddb08b186570ac5a2e
Source dataset
uspto-grants-1999_10
Patent number
US05968962

Reaction notes

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