2,4-Di-tert-butylphenol → Methyl (2R)-2-(2,4-Di-t-butylphenyloxy)propanate

HRID 248194Notes

Reaction equation

HRID 248194 reaction equation
C(=O)([O-])[O-].[K+].[K+].[C:7]([C:11]1[CH:16]=[C:15]([C:17]([CH3:20])([CH3:19])[CH3:18])[CH:14]=[CH:13][C:12]=1[OH:21])([CH3:10])([CH3:9])[CH3:8].C1(S(O[C@@H:32]([CH3:37])[C:33]([O:35][CH3:36])=[O:34])(=O)=O)C=CC=CC=1>CS(C)=O>[C:7]([C:11]1[CH:16]=[C:15]([C:17]([CH3:20])([CH3:19])[CH3:18])[CH:14]=[CH:13][C:12]=1[O:21][C@H:32]([CH3:37])[C:33]([O:35][CH3:36])=[O:34])([CH3:10])([CH3:9])[CH3:8]

Participants

5

Reactant 3

HCID 73112,4-Di-tert-butylphenolHCID 11430Potassium CarbonateHCID 57260475Methyl (2S)-2-(Phenylsulfonyl)oxypropanate

Product 1

HCID 54175729Methyl (2R)-2-(2,4-Di-t-butylphenyloxy)propanateYield 84.2%

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent2×

Procedure

Potassium carbonate (5.66 g, 41 mmol) and 2,4-di-t-butylphenol (8.87 g, 43 mmol) were dissolved in dimethyl sulfoxide (175 mL) at 25° C. and allowed to stir overnight under a nitrogen atmosphere to ensure complete anion formation. A solution of 10.0 g (41 mmol) of methyl (2S)-2-(phenylsulfonyl)oxypropanate (12) in dimethyl sulfoxide (50 mL) was added to the anion at 25° C. and the reaction mixture was allowed to stir overnight. The reaction was quenched with water (200 mL) and the phases were separated. The aqueous phase was extracted with perchloroethylene (3×200 mL). The combined organic extracts were washed with water (3×300 mL), a saturated aqueous sodium chloride solution (1×300 mL) and dried (MgSO4). Concentration and purification by flash chromatography on silica gel (EM silica gel 60, 0.040-0.063 partical size, 230-400 Mesh, column size: 7 cm diameter×18 cm length) using hexane and ethyl acetate (29:1) afforded 10.1 g (77%) of methyl (2R)-2-(2,4-di-t-butylphenyloxy)propanate (17) as a thick oil: 1H NMR (CDCl3) δ1.29 (s, 9 H), 1.43 (s, 9 H), 1.60-1.65 (d, 3 H), 3.73 (s, 3 H), 4.75-4.82 (q, 1 H), 6.54-6.57 (d, 1 H), 7.08-7.12 (d, 1 H), 7.33 (s, 1 H); 13C NMR (CDCl3) δ172.9, 153.7, 143.0, 137.2, 124.2, 123.1, 110.5, 71.7, 52.0, 5.0, 34.2, 31.5, 29.9, 18.6; IR (neat) 2962 (vs), 1764 (s), 1740 (s), 1497 (s), 1235 (vs) cm-1.

Workup

  1. stirringto stir overnight
  2. customThe reaction was quenched with water (200 mL)
  3. customthe phases were separated
  4. extractionThe aqueous phase was extracted with perchloroethylene (3×200 mL)
  5. washThe combined organic extracts were washed with water (3×300 mL)
  6. dry with materiala saturated aqueous sodium chloride solution (1×300 mL) and dried (MgSO4)
  7. concentrationConcentration and purification by flash chromatography on silica gel (EM silica gel 60, 0.040-0.063 partical size, 230-400 Mesh, column size: 7 cm diameter×18 cm length)

Sources & evidence

ORD record
ord-0fddf0f5ba564ffba18554a38a2f6226
Source dataset
uspto-grants-1993_05
Patent number
US05208345

Reaction notes

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