4-Toluenesulfonyl chloride → 4-(4-Bromophenoxy)-2-(hydroxymethyl)butyl 4-methylbenzenesulfonate

HRID 338531Notes

Reaction equation

HRID 338531 reaction equation
[H-].[Na+].[Br:3][C:4]1[CH:17]=[CH:16][C:7]([O:8][CH2:9][CH2:10][CH:11]([CH2:14][OH:15])[CH2:12][OH:13])=[CH:6][CH:5]=1.[S:18](Cl)([C:21]1[CH:27]=[CH:26][C:24]([CH3:25])=[CH:23][CH:22]=1)(=[O:20])=[O:19]>O1CCCC1>[CH3:25][C:24]1[CH:26]=[CH:27][C:21]([S:18]([O:13][CH2:12][CH:11]([CH2:14][OH:15])[CH2:10][CH2:9][O:8][C:7]2[CH:6]=[CH:5][C:4]([Br:3])=[CH:17][CH:16]=2)(=[O:20])=[O:19])=[CH:22][CH:23]=1

Participants

5

Reactant 3

HCID 73974-Toluenesulfonyl chlorideHCID 24758Sodium hydrideHCID 794507012-(2-(4-Bromophenoxy)ethyl)propane-1,3-diol

Product 1

HCID 866988534-(4-Bromophenoxy)-2-(hydroxymethyl)butyl 4-methylbenzenesulfonateYield 46%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a suspension of NaH (0.11 g, 4.58 mmol) in anhydrous tetrahydrofuran (10 mL) was added a solution of 2-(2-(4-bromophenoxy)ethyl)propane-1,3-diol (0.63 g, 2.29 mmol) in anhydrous tetrahydrofuran (10 mL) dropwise. The reaction mixture was stirred at room temperature for 30 minutes. Then, tosyl chloride (0.44 g, 2.3 mmol) was added in portions. The reaction mixture was then stirred at room temperature for 2 hours. The reaction mixture was carefully quenched with water and extracted with ethyl acetate (4×30 mL). The combined organic layers were dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to give the crude product, which was purified by flash chromatography (0-35% ethyl acetate/petroleum ether) to afford the title compound (0.45 g, 46%) as white solid. 1H NMR (400 MHz, CDCl3) ppm 7.80 (d, 2H), 7.40-7.30 (m, 4H), 6.71 (d, 2H), 4.21-4.09 (m, 2H), 4.00-3.90 (m, 2H), 3.74-3.62 (m, 2H), 2.45 (s, 3H), 2.14 (m, 1H), 1.89-1.74 (m, 3H).

Workup

  1. stirringThe reaction mixture was then stirred at room temperature for 2 hours
  2. customThe reaction mixture was carefully quenched with water
  3. extractionextracted with ethyl acetate (4×30 mL)
  4. dry with materialThe combined organic layers were dried over anhydrous sodium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure
  7. customto give the crude product, which
  8. customwas purified by flash chromatography (0-35% ethyl acetate/petroleum ether)

Sources & evidence

ORD record
ord-872da749a3c1423e8179cc4c47e2a8e5
Source dataset
uspto-grants-2014_11
Patent number
US08889730B2

Reaction notes

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