Allyl bromide → Methyl 2-allyloxy-4-(1-tertbutyloxycarbonyl-4-piperidinyloxy)benzoate

HRID 1377715Notes

Reaction equation

HRID 1377715 reaction equation
[OH:1][C:2]1[CH:11]=[C:10]([O:12][CH:13]2[CH2:18][CH2:17][N:16]([C:19]([O:21][C:22]([CH3:25])([CH3:24])[CH3:23])=[O:20])[CH2:15][CH2:14]2)[CH:9]=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5].[H-].[Na+].[CH2:28](Br)[CH:29]=[CH2:30]>CN(C=O)C>[CH2:30]([O:1][C:2]1[CH:11]=[C:10]([O:12][CH:13]2[CH2:18][CH2:17][N:16]([C:19]([O:21][C:22]([CH3:25])([CH3:24])[CH3:23])=[O:20])[CH2:15][CH2:14]2)[CH:9]=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5])[CH:29]=[CH2:28]

Participants

5

Reactant 3

HCID 7841Allyl bromideHCID 24758Sodium hydrideHCID 105940774-(N-t-Butoxycarbonyl-4-piperidinyloxy)-2-hydroxybenzoic acid methyl ester

Product 1

HCID 22914690Methyl 2-allyloxy-4-(1-tertbutyloxycarbonyl-4-piperidinyloxy)benzoate

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a stirred solution of methyl 2-hydroxy-4-(1-tertbutyloxycarbonyl-4-piperidinyloxy)benzoate from Step XX of Example XX (2.50 g, 7.11 mmol) in DMF (50 mL) under N2 was added NaH (427 mg, 10.7 mmol). The reaction mixture was cooled, and allyl bromide (1.23 mL, 14.2 mmol) was added via syringe. The reaction mixture was allowed to warm to ambient temperature and stirred for 2 hours. The solvent was removed under reduced pressure and the residue partitioned between ethyl acetate and aqueous NaHCO3. The ethyl acetate layer was dried (MgSO4), filtered, and evaporated under reduced pressure. The residue was purified using pressurized silica gel column chromatography using a gradient elution of 10-15% ethyl acetate in hexanes. Methyl 2-allyloxy-4-(1-tertbutyloxycarbonyl-4-piperidinyloxy)benzoate was obtained as a thick colorless oil.

Workup

  1. temperatureThe reaction mixture was cooled
  2. customThe solvent was removed under reduced pressure
  3. customthe residue partitioned between ethyl acetate and aqueous NaHCO3
  4. dry with materialThe ethyl acetate layer was dried (MgSO4)
  5. filtrationfiltered
  6. customevaporated under reduced pressure
  7. customThe residue was purified
  8. washa gradient elution of 10-15% ethyl acetate in hexanes

Sources & evidence

ORD record
ord-c9760e516e1b4989b6c24af0287449e7
Source dataset
uspto-grants-1997_09
Patent number
US05665719

Reaction notes

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