4-Toluenesulfonyl chloride → 4,4,4-Trifluorobutyl 4-methylbenzenesulfonate

HRID 536758Notes

Reaction equation

HRID 536758 reaction equation
[F:1][C:2]([F:8])([F:7])[CH2:3][CH2:4][CH2:5][OH:6].[C:9]1([CH3:19])[CH:14]=[CH:13][C:12]([S:15](Cl)(=[O:17])=[O:16])=[CH:11][CH:10]=1>C(Cl)Cl.N1C=CC=CC=1.CN(C)C1C=CN=CC=1>[CH3:19][C:9]1[CH:14]=[CH:13][C:12]([S:15]([O:6][CH2:5][CH2:4][CH2:3][C:2]([F:8])([F:7])[F:1])(=[O:17])=[O:16])=[CH:11][CH:10]=1

Participants

6

Reactant 2

HCID 73974-Toluenesulfonyl chlorideHCID 1363074,4,4-Trifluorobutan-1-ol

Product 1

HCID 136207474,4,4-Trifluorobutyl 4-methylbenzenesulfonateYield 45.4%

Reagents, catalysts & solvents 3

HCID 142844-(Dimethylamino)pyridineCatalystHCID 1049PyridineSolventHCID 6344DichloromethaneSolvent

Procedure

To a solution of 4,4,4-trifluorobutan-1-ol (5.0 g, 39.0 mmol) in CH2Cl2 (30 mL) and pyridine (20 mL) was added 4-(dimethylamino)pyridine (0.24 g, 2.0 mmol) followed by p-toluenesulfonyl chloride (7.4 g, 39.0 mmol). The mixture was allowed to stir at ambient temperature for 20 hours then was quenched with 5% aqueous HCl (20 mL) and the layers were separated. The aqueous phase was extracted with CH2Cl2 (3×5 mL). The combined organic extracts were dried over Na2SO4, filtered and concentrated under reduced pressure. Purification by column chromatography (SiO2, 75% hexanes in EtOAc) afforded the title compound (5.0 g, 17.7 mmol, 45% yield). 1H NMR (300 MHz, CDCl3) δ ppm 1.86-1.98 (m, 2H) 2.06-2.24 (m, 2H) 2.46 (s, 3H) 4.09 (t, J=5.9 Hz, 2H) 7.37 (d, J=7.8 Hz, 2H) 7.79 (d, J=8.5 Hz, 2H).

Workup

  1. customthen was quenched with 5% aqueous HCl (20 mL)
  2. customthe layers were separated
  3. extractionThe aqueous phase was extracted with CH2Cl2 (3×5 mL)
  4. dry with materialThe combined organic extracts were dried over Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure
  7. customPurification by column chromatography (SiO2, 75% hexanes in EtOAc)

Sources & evidence

ORD record
ord-acfee631408047dda2c720a2dbd643bc
Source dataset
uspto-grants-2014_10
Patent number
US08859596B2

Reaction notes

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