p-Toluenesulfonic acid → HCID 21938505, compound

HRID 858793Notes

Reaction equation

HRID 858793 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([C:8](=[O:10])[CH3:9])=[C:4]([Cl:11])[CH:3]=1.[CH2:12]([O:14]C(OCC)OCC)[CH3:13].CC1C=CC(S(O)(=O)=O)=CC=1.C([O-])(O)=O.[Na+]>C(O)CO>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2([CH3:9])[O:14][CH2:12][CH2:13][O:10]2)=[C:4]([Cl:11])[CH:3]=1

Participants

6

Reactant 4

HCID 6101p-Toluenesulfonic acidHCID 31214Ethyl orthoformateHCID 516892Sodium BicarbonateHCID 155609501-(4-Bromo-2-chlorophenyl)ethan-1-one

Product 1

HCID 21938505HCID 21938505, compound

Reagents, catalysts & solvents 1

HCID 174Ethylene GlycolSolvent

Procedure

1-(4-Bromo-2-chloro-phenyl)-ethanone (from step 2 below) (1.86 g, 5.66 mmol), below was dissolved in ethylene glycol (5 mL). Triethylorthoformate (0.71 g, 4.79 mmol), and tosic acid (0.02 g) were added and reaction was stirred under nitrogen for 24 hours at room temperature. The resulting reaction mixture was poured into NaHCO3 (10 mL) and extracted with EtOAC. The combined organics were washed with water (10 mL) and brine (10 mL) then dried over Na2SO4, filtered and concentrated. The crude residue was purified by flash chromatography (5% EtOAc in Hexanes) to yield the intermediate ether as a colorless oil (0.69 g, 58%). 1H NMR (CDCl3): δ 1.77 (s, 3H), 3.74–3.79 (m, 2H), 4.04–4.09 (m, 2H), 7.37 (dd, J=8.5, 1.9 Hz, 1H), 7.52 (d, J=8.5 Hz, 1H), 7.55 (d, J=1.9 Hz, 1H). ESIMS (MH+): 278.2.

Workup

  1. customreaction
  2. customThe resulting reaction mixture
  3. extractionextracted with EtOAC
  4. washThe combined organics were washed with water (10 mL) and brine (10 mL)
  5. dry with materialthen dried over Na2SO4
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customThe crude residue was purified by flash chromatography (5% EtOAc in Hexanes)
  9. customto yield the intermediate ether as a colorless oil (0.69 g, 58%)

Sources & evidence

ORD record
ord-58abe215e07143f4a70df89b19c626f6
Source dataset
uspto-grants-2006_12
Patent number
US07148226B2

Reaction notes

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