Carbon Tetrachloride → 1-(Chloromethyl)-3-methanesulfonylbenzene

HRID 1644692Notes

Reaction equation

HRID 1644692 reaction equation
C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[C:20]([Cl:24])(Cl)(Cl)Cl.[CH3:25][S:26]([C:29]1[CH:30]=[C:31](CO)[CH:32]=[CH:33][CH:34]=1)(=[O:28])=[O:27]>O1CCCC1>[CH3:25][S:26]([C:29]1[CH:34]=[C:33]([CH:32]=[CH:31][CH:30]=1)[CH2:20][Cl:24])(=[O:28])=[O:27]

Participants

5

Reactant 3

HCID 5943Carbon TetrachlorideHCID 11776TriphenylphosphineHCID 23549738(3-Methanesulfonylphenyl)methanol

Product 1

HCID 220504111-(Chloromethyl)-3-methanesulfonylbenzeneYield 77.2%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

Triphenylphosphine (7.5 g, 29 mmol), carbon tetrachloride (11.0 mL, 114 mmol) and tetrahydrofuran (18 mL) were combined and stirred at room temperature for 10 minutes. A suspension of (3-methanesulfonyl-phenyl)-methanol (2.68 g, 14.3 mmol) in 18 mL tetrahydrofuran was added, then the reaction mixture was heated at 75° C. for 3 hours. The reaction mixture was cooled to room temperature, then partitioned between ethyl acetate and water. The organic phase was dried over MgSO4, filtered, and concentrated to give the crude product as an oily solid. A solution of this crude product and dichloromethane was evaporated over silica gel, and the resulting silica gel supported crude product was loaded onto an Analogix SuperFlash™ column. Flash chromatography (15%-35% ethyl acetate in hexanes) afforded 2.26 g (77%) of 3-(methanesulfonyl)benzyl chloride as a white solid. 1H NMR (300 MHz, DMSO-d6) δ ppm 8.01 (s, 1 H), 7.91 (d, J=7.8 Hz, 1 H), 7.81 (d, J=7.8 Hz, 1 H), 7.68 (t, J=7.8 Hz, 1 H), 4.90 (s, 2 H), 3.24 (s, 3 H). HRMS (EI+) cald. for C8H9ClO2S [M+] 204.0012, obsd. 204.0012.

Workup

  1. additionwas added
  2. temperaturethe reaction mixture was heated at 75° C. for 3 hours
  3. temperatureThe reaction mixture was cooled to room temperature
  4. custompartitioned between ethyl acetate and water
  5. dry with materialThe organic phase was dried over MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customto give the crude product as an oily solid
  9. customA solution of this crude product and dichloromethane was evaporated over silica gel

Sources & evidence

ORD record
ord-80f22763d3c44d76977f64b525ef2f2b
Source dataset
uspto-grants-2012_02
Patent number
US08124629B2

Reaction notes

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