4-Toluenesulfonyl chloride → HCID 131732214, compound

HRID 1410653Notes

Reaction equation

HRID 1410653 reaction equation
[O:1]1[CH2:5][CH2:4][O:3][CH:2]1[CH2:6][CH2:7][CH2:8][CH2:9][OH:10].C(N(CC)CC)C.[C:18]1([CH3:28])[CH:23]=[CH:22][C:21]([S:24](Cl)(=[O:26])=[O:25])=[CH:20][CH:19]=1>C(Cl)Cl.CN(C)C1C=CN=CC=1>[CH3:28][C:18]1[CH:23]=[CH:22][C:21]([S:24]([O:10][CH2:9][CH2:8][CH2:7][CH2:6][CH:2]2[O:3][CH2:4][CH2:5][O:1]2)(=[O:26])=[O:25])=[CH:20][CH:19]=1

Participants

6

Reactant 3

HCID 73974-Toluenesulfonyl chlorideHCID 8471TriethylamineHCID 13027284HCID 13027284, compound

Product 1

HCID 131732214HCID 131732214, compound

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6344DichloromethaneSolvent2×

Procedure

To a stirred solution of the alcohol of step 4 (0.50 g, 3.4 mmol, 1.0 equiv.) in CH2Cl2 (50 mL) at room temperature was added triethylamine (0.62 mL, 4.4 mmol, 1.3 equiv.) followed by p-toluenesulfonylchloride (TsCl, 0.71 g, 3.7 mmol, 1.1 equiv.) and 4-dimethylaminopyridine (50 mg, 0.4 mmol, 0.1 equiv.). The resulting mixture was stirred at that temperature for 8 h. The mixture was diluted with CH2Cl2 (100 mL) washed with sat. aq. NaHCO3 (100 mL) and brine (2×100 mL), dried (MgSO4), filtered, and concentrated under reduced pressure. While concentrating, the temperature was maintained below 40° C., as the compound had been reported as unstable above this temperature (Wennekes et al. 2008). Due to this instability, the compound was used in the next step crude. 1H NMR (500 MHz, CDCl3) δ=7.79 (d, J=8.3 Hz, 2H), 7.34 (d, J=8.4 Hz, 2H), 4.80 (t, J=4.6 Hz, 1H), 4.03 (t, J=6.5 Hz, 2H), 3.96-3.88 (m, 2H), 3.87-3.78 (m, 2H), 2.45 (s, 3H), 1.75-1.65 (m, 2H), 1.65-1.57 (m, 2H), 1.50-1.41 (m, 2H) ppm; 13C NMR (125 MHz, CDCl3) δ=144.9, 133.5, 130.0, 128.1, 104.4, 70.6, 65.1, 33.3, 29.0, 20.1, 14.4 ppm.

Workup

  1. washwashed with sat. aq. NaHCO3 (100 mL) and brine (2×100 mL)
  2. dry with materialdried (MgSO4)
  3. filtrationfiltered
  4. concentrationconcentrated under reduced pressure
  5. concentrationWhile concentrating
  6. temperaturethe temperature was maintained below 40° C., as the compound

Sources & evidence

ORD record
ord-08667fbda6084299adca51da88c4f011
Source dataset
uspto-grants-2014_12
Patent number
US08921568B2

Reaction notes

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