Salicylic Acid → Tert-butyl 2-hydroxybenzoate

HRID 1259024Notes

Reaction equation

HRID 1259024 reaction equation
C1N=CN(C(N2C=NC=C2)=O)C=1.[C:13]([OH:22])(=[O:21])[C:14]1[C:15](=[CH:17][CH:18]=[CH:19][CH:20]=1)[OH:16].[C:23](O)([CH3:26])([CH3:25])[CH3:24].C1CCN2C(=NCCC2)CC1.C([O-])(O)=O.[Na+]>CN(C=O)C>[OH:16][C:15]1[CH:17]=[CH:18][CH:19]=[CH:20][C:14]=1[C:13]([O:22][C:23]([CH3:26])([CH3:25])[CH3:24])=[O:21]

Participants

7

Reactant 5

HCID 338Salicylic AcidHCID 6386tert-ButanolHCID 682631,1'-CarbonyldiimidazoleHCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 516892Sodium Bicarbonate

Product 1

HCID 11424104Tert-butyl 2-hydroxybenzoateYield 73.6%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
50 °C

Procedure

CDI (2.40 g, 14.79 mmol) was added to a solution of salicylic acid (2.02 g, 14.62 mmol) in DMF (20 mL). The reaction mixture was stirred at 50° C. for 30 min and tert-butyl alcohol (2.80 mL, 29.84 mmol) and DBU (4.4 mL, 29.45 mmol) were dropwise added. The reaction mixture was stirred at 50° C. for 16 h and allowed to reach r.t. It was poured into NaHCO3 (100 mL, saturated aqueous solution) and extracted with EtOAc (70 mL). The organic layer was dried over Na2SO4 (anhydrous), filtered and concentrated. The crude residue was flash chromatographed on SiO2 (5% EtOAc/hexanes) to furnish 2.089 g of tert-butyl 2-hydroxybenzoate (colourless oil, yield: 73%).

Workup

  1. stirringThe reaction mixture was stirred at 50° C. for 16 h
  2. customto reach r.t
  3. extractionextracted with EtOAc (70 mL)
  4. dry with materialThe organic layer was dried over Na2SO4 (anhydrous)
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customchromatographed on SiO2 (5% EtOAc/hexanes)

Sources & evidence

ORD record
ord-ec27da2a6435400da8db9b08315306f2
Source dataset
uspto-grants-2013_06
Patent number
US08466197B2

Reaction notes

Loading…