4-Toluenesulfonyl chloride → (2S)-2-hydroxy-3,3-dimethylbutyl 4-methylbenzenesulfonate

HRID 1182274Notes

Reaction equation

HRID 1182274 reaction equation
[CH3:1][C:2]([CH3:8])([CH3:7])[C@H:3]([OH:6])[CH2:4][OH:5].[C:9]1([CH3:19])[CH:14]=[CH:13][C:12]([S:15](Cl)(=[O:17])=[O:16])=[CH:11][CH:10]=1>N1C=CC=CC=1>[CH3:19][C:9]1[CH:14]=[CH:13][C:12]([S:15]([O:5][CH2:4][C@@H:3]([OH:6])[C:2]([CH3:8])([CH3:7])[CH3:1])(=[O:17])=[O:16])=[CH:11][CH:10]=1

Participants

4

Reactant 2

HCID 73974-Toluenesulfonyl chlorideHCID 6951684(2S)-3,3-dimethylbutane-1,2-diol

Product 1

HCID 15692141(2S)-2-hydroxy-3,3-dimethylbutyl 4-methylbenzenesulfonateYield 85.2%

Reagents, catalysts & solvents 1

HCID 1049PyridineSolvent2×

Conditions

Temperature
0 °C

Procedure

To 6.65 g (56 mmol) of (2S)-3,3-dimethyl-1,2-butanediol in 13 mL of pyridine at 0° C. was added dropwise a solution of 10.68 g (56 mmol) of p-toluenesulfonyl chloride in 20 mL of pyridine. The solution was maintained at 0° C. for 5 h and then let warm to ambient temperature. After being stirred overnight, the mixture was concentrated, and the residue was taken up in 200 mL of diethyl ether. The ether solution was washed with 50 mL of 1N hydrochloric acid, 50 mL of saturated aqueous sodium bicarbonate, and 50 mL of water, dried over anhydrous magnesium sulfate, and concentrated. The residue was purified by silica gel chromatography eluting with ethyl acetate:hexanes (3.5:6.5) to give 13 g (85%) of (2S)-2-hydroxy-3,3-dimethylbutyl 4-methylbenzenesulfonate. 1H-NMR (300 MHz, DMSO-d6): δ 7.79 (d, J=8 Hz, 2H), 7.47 (d, J=8 Hz, 2H), 5.11 (br s, 1H), 4.08 (dd, J=10 Hz, J=3 Hz, 1H), 3.76 (dd, J=10 Hz, J=8 Hz, 1H), 3.23 (d, J=8 Hz, 1H), 2.41 (s, 3H), 0.76 (s, 9H). ES-LCMS m/z 273 (M+H), 295 (M+Na).

Workup

  1. temperaturelet warm to ambient temperature
  2. concentrationthe mixture was concentrated
  3. washThe ether solution was washed with 50 mL of 1N hydrochloric acid, 50 mL of saturated aqueous sodium bicarbonate, and 50 mL of water
  4. dry with materialdried over anhydrous magnesium sulfate
  5. concentrationconcentrated
  6. customThe residue was purified by silica gel chromatography
  7. washeluting with ethyl acetate:hexanes (3.5:6.5)

Sources & evidence

ORD record
ord-cc75b7dc0e2e4a7484b6e7c9cd84269d
Source dataset
uspto-grants-2007_10
Patent number
US07288541B2

Reaction notes

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