4-Toluenesulfonyl chloride → HCID 86698787, compound

HRID 338453Notes

Reaction equation

HRID 338453 reaction equation
[CH2:1]([O:8][CH2:9][C:10]([C:15]1[CH:20]=[CH:19][C:18]([Br:21])=[CH:17][CH:16]=1)([CH2:13][OH:14])[CH2:11]O)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[Li]CCCC.C1(C)C=CC(S(Cl)(=O)=O)=CC=1>C1COCC1.C(OCC)C>[CH2:1]([O:8][CH2:9][C:10]1([C:15]2[CH:20]=[CH:19][C:18]([Br:21])=[CH:17][CH:16]=2)[CH2:13][O:14][CH2:11]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

6

Reactant 3

HCID 73974-Toluenesulfonyl chlorideHCID 86698785HCID 86698785, compoundHCID 178418339Butyllithium2×

Product 1

HCID 86698787HCID 86698787, compoundYield 57.4%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

To a solution of 2-Benzyloxymethyl-2-(4-bromo-phenyl)-propane-1,3-diol (475 mg, 1.35 mmol) in THF (5 mL) at 0° C. was added nBuLi (0.54 mL, 2.5M in hexanes, 1.35 mmol). The reaction mixture was stirred for 30 minutes at 0° C., at which point a solution of p-toluenesulfonyl chloride (258 mg, 1.35 mmol) in THF (5 mL) was added via syringe. The reaction mixture was stirred for 1 hour at 0° C. and nBuLi (0.54 mL, 2.5M in hexanes, 1.35 mmol) was added. The reaction mixture was stirred at 60° C. for 16 hours. The reaction mixture was cooled to room temperature, diluted with ethyl ether (100 mL) and washed with water (50 mL). The aqueous layer was extracted with ethyl ether (2×50 mL). The combined organics were dried over magnesium sulfate, filtered and concentrated in vacuo to afford 477 mg cloudy beige oil. The crude oil was purified by flash chromatography (12 g silica, 0-50% ethyl acetate/heptane, 26 column volumes). Product fractions were combined and concentrated in vacuo to afford the title compound as a colorless oil (258 mg, 57% yield).

Workup

  1. additionwas added via syringe
  2. stirringThe reaction mixture was stirred at 60° C. for 16 hours
  3. temperatureThe reaction mixture was cooled to room temperature
  4. washwashed with water (50 mL)
  5. extractionThe aqueous layer was extracted with ethyl ether (2×50 mL)
  6. dry with materialThe combined organics were dried over magnesium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. customto afford 477 mg cloudy beige oil
  10. customThe crude oil was purified by flash chromatography (12 g silica, 0-50% ethyl acetate/heptane, 26 column volumes)
  11. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-779b83817f314673a17b8250007c2845
Source dataset
uspto-grants-2014_11
Patent number
US08889730B2

Reaction notes

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