4-Toluenesulfonyl chloride → HCID 86695317, compound

HRID 879048Notes

Reaction equation

HRID 879048 reaction equation
[CH2:1]([OH:16])[CH2:2][CH2:3]/[CH:4]=[CH:5]\[CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH3:15].CCN(CC)CC.[C:24]1([CH3:34])[CH:29]=[CH:28][C:27]([S:30](Cl)(=[O:32])=[O:31])=[CH:26][CH:25]=1.C([O-])(O)=O.[Na+]>CN(C)C1C=CN=CC=1.C(Cl)Cl.C(OCC)(=O)C>[CH3:34][C:24]1[CH:29]=[CH:28][C:27]([S:30]([O:16]/[CH:1]=[CH:2]\[CH2:3][CH:4]=[CH:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH3:15])(=[O:32])=[O:31])=[CH:26][CH:25]=1

Participants

8

Reactant 4

HCID 73974-Toluenesulfonyl chlorideHCID 8471TriethylamineHCID 516892Sodium BicarbonateHCID 1100967940642-44-2

Product 1

HCID 86695317HCID 86695317, compoundYield 84.7%

Reagents, catalysts & solvents 3

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6344DichloromethaneSolvent2×HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

A 10 mL round bottom flask was charged with 21 (0.48 g, 2.12 mmol), Et3N (590 μL, 4.24 mmol), 4-dimethylaminopyridine (0.03 g, 0.21 mmol), and CH2Cl2 (5 mL) under an argon atmosphere. The solution was cooled to 0° C., and a solution of 4-toluenesulfonyl chloride (0.61 g, 3.18 mmol) in CH2Cl2 (1 mL) was added drop wise. The mixture was stirred vigourously for 4 hours at room temperature. The reaction mixture was treated with saturated aqueous NaHCO3 (10 mL). After stirring at room temperature for 20 minutes, ethyl acetate (20 mL) was added. The organic layer was separated and washed with water (3×100 mL) and brine (50 mL), and dried over MgSO4. The solution was filtered and the solvent was removed in vacuo. Flash chromatography of the residue (SiO2, using a gradient of 2:1 hexanes/CH2Cl2 to 1:1 hexanes/CH2Cl2) provided 22 (0.68 g, 84% yield, 84% Z as determined by 13C-NMR) as a colorless oil; 1H NMR (CDCl3): δ 7.79 (2H, d, J=8.3 Hz), 7.33 (2H, d, J=8.9 Hz), 5.19-5.40 (2H, m), 4.02 2H, t, J=6.4 Hz), 2.44 (3H, s), 1.91-2.08 (4H, m), 1.66-1.71 (2H, m), 1.25 (16H, m), 0.88 (3H, t, J=7.0 Hz); 13C NMR (100 Hz, CDCl3): δ 144.8, 144.7, 133.3, 131.8, 129.9, 128.0, 127.8, 127.4, 70.2, 32.6, 32.0, 29.7 (2C), 29.6 (2C), 29.5, 29.4, 29.0, 27.3, 23.1, 22.8, 14.3; HRMS (FAB): 381.2477, [C22H36O3S+H]+ requires 381.2458.

Workup

  1. stirringAfter stirring at room temperature for 20 minutes
  2. customThe organic layer was separated
  3. washwashed with water (3×100 mL) and brine (50 mL)
  4. dry with materialdried over MgSO4
  5. filtrationThe solution was filtered
  6. customthe solvent was removed in vacuo

Sources & evidence

ORD record
ord-9a6d5fabd4f840989746afa8d6f7bda3
Source dataset
uspto-grants-2015_03
Patent number
US08987531B2

Reaction notes

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