4-Hydroxybenzaldehyde → Tert-butyl 2-(4-formylphenoxy)acetate

HRID 40534Notes

Reaction equation

HRID 40534 reaction equation
[OH:1][C:2]1[CH:9]=[CH:8][C:5]([CH:6]=[O:7])=[CH:4][CH:3]=1.C([O-])([O-])=O.[K+].[K+].[Na+].[I-].Br[CH2:19][C:20]([O:22][C:23]([CH3:26])([CH3:25])[CH3:24])=[O:21]>C(#N)C.C(Cl)Cl.O>[C:23]([O:22][C:20]([CH2:19][O:1][C:2]1[CH:9]=[CH:8][C:5]([CH:6]=[O:7])=[CH:4][CH:3]=1)=[O:21])([CH3:26])([CH3:25])[CH3:24]

Participants

8

Reactant 4

HCID 1264-HydroxybenzaldehydeHCID 5238Sodium IodideHCID 11430Potassium CarbonateHCID 79177tert-Butyl bromoacetate

Product 1

HCID 639902Tert-butyl 2-(4-formylphenoxy)acetateYield 92.3%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6342AcetonitrileSolventHCID 6344DichloromethaneSolvent

Procedure

A solution of 4-hydroxybenzaldehyde (2.44 g, 20.0 mmol) in dry acetonitrile (8.0 mL) was treated with powdered, dried K2CO3 (3.04 g, 22.0 mmol) and NaI (304 mg, 2.00 mmol). The mixture was refluxed under argon for 30 min. tert-Butyl bromoacetate (1.48 mL, 1.95 g, 10.0 mmol) was added dropwise, and the reflux was continued for 12 h. Water and CH2Cl2 were added and the phases were separated. The aqueous layer was extracted with CH2Cl2. The combined organic phase was washed with water. The organic layer was dried (Na2SO4). Evaporation of the solvent and chromatography of the oily residue [silica, ethyl acetate/hexanes (3:7)] afforded a white, crystalline solid (2.18 g, 92%): mp 56-57° C.; IR (film, νmax cm−1) 1762, 1752, 1685, 1600; 1H NMR δ 1.48 (s, 9H), 4.60 (s, 2H), 6.99 (d, J=8.7 Hz, 2H), 7.84 (d, J=8.7 Hz, 2H), 9.89 (s, 1H); 13C NMR δ 28.25, 65.76, 83.17, 115.08, 130.82, 132.18, 163.00, 167.37, 190.98; EI-MS 105/107, 135, 193/194, 236/237; FAB-MS obsd 237.1120, calcd 237.1127 [(M+H)+, M=C13H16O4]; Anal. Calcd C, 66.09; H, 6.83. Found C, 66.06; H, 6.82.

Workup

  1. additionwas added dropwise
  2. customthe phases were separated
  3. extractionThe aqueous layer was extracted with CH2Cl2
  4. washThe combined organic phase was washed with water
  5. dry with materialThe organic layer was dried (Na2SO4)
  6. customEvaporation of the solvent and chromatography of the oily residue [silica, ethyl acetate/hexanes (3:7)]

Sources & evidence

ORD record
ord-b38b6b354b334543adbe07aa208f07ca
Source dataset
uspto-grants-2013_09
Patent number
US08530459B2

Reaction notes

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