Dimethyl Sulfoxide → HCID 68156788, compound

HRID 537448Notes

Reaction equation

HRID 537448 reaction equation
[OH:1][CH:2]([C:7]1[CH:17]=[CH:16][C:10]([C:11]([O:13][CH2:14][CH3:15])=[O:12])=[CH:9][CH:8]=1)[CH2:3][CH:4]([CH3:6])[CH3:5].ClCCl.CS(C)=O.C(N(CC)CC)C>[Cl-].[Na+].O>[CH3:6][CH:4]([CH3:5])[CH2:3][C:2]([C:7]1[CH:8]=[CH:9][C:10]([C:11]([O:13][CH2:14][CH3:15])=[O:12])=[CH:16][CH:17]=1)=[O:1]

Participants

6

Reactant 4

HCID 679Dimethyl SulfoxideHCID 6344DichloromethaneHCID 8471TriethylamineHCID 68156815HCID 68156815, compound

Product 1

HCID 68156788HCID 68156788, compoundYield 81.3%

Reagents, catalysts & solvents 1

HCID 57417360Sodium chloride; waterSolvent

Conditions

Temperature
0 °C

Procedure

A mixture of ethyl 4-(1-hydroxy-3-methylbutyl)benzoate (15 g, 63 mmol), dichloromethane (150 mL), dimethylsulfoxide (198 g, 2540 mmol), and triethylamine (32 g, 317 mmol) was cooled to 0° C. Sulfur trioxide pyridine complex (30 g, 190 mmol) was added in portions, maintaining the internal temperature below 50° C. The mixture was stirred at 0° C. for 1 hour. The reaction was then allowed to warm to room temperature and stir for 36 hours. The reaction was diluted with brine (300 mL) and extracted with methyl tert-butylether (2×500 mL). The combined organics were washed with 1 N aqueous hydrochloric acid (500 mL), dried over sodium sulfate, filtered, and concentrated. Purification by flash column chromatography gave ethyl 4-(3-methylbutanoyl)benzoate (12 g, 80%) as a white solid. 1H NMR (400 MHz, CDCl3, δ): 8.11 (dd, J=1.6, 6.8 Hz, 2H), 7.98 (d, J=6.8 Hz, 2H), 4.40 (q, J=7.2 Hz, 2H), 2.85 (d, J=6.8 Hz, 2H), 2.24-2.34 (m, 1H), 1.39-1.43 (t, J=7.2 Hz, 3H), 1.50 (d, J=6.8 Hz, 6H).

Workup

  1. additionSulfur trioxide pyridine complex (30 g, 190 mmol) was added in portions
  2. temperaturemaintaining the internal temperature below 50° C
  3. temperatureto warm to room temperature
  4. stirringstir for 36 hours
  5. extractionextracted with methyl tert-butylether (2×500 mL)
  6. washThe combined organics were washed with 1 N aqueous hydrochloric acid (500 mL)
  7. dry with materialdried over sodium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customPurification by flash column chromatography

Sources & evidence

ORD record
ord-1444e80c25b745ea8c360d92ab410f09
Source dataset
uspto-grants-2014_10
Patent number
US08859591B2

Reaction notes

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