Bromine → 6-Methoxy-2-(4-methoxyphenyl)benzo[b]thiophene

HRID 1638127Notes

Reaction equation

HRID 1638127 reaction equation
O.C1(C)C=CC(S(O)(=O)=O)=CC=1.BrBr.[C:15]1([C:23]([CH2:25][C:26]2[CH:33]=[CH:32][C:29]([O:30][CH3:31])=[CH:28][CH:27]=2)=[S:24])[CH:22]=[CH:21][C:18]([O:19][CH3:20])=[CH:17][CH:16]=1>ClC1C=CC=CC=1>[CH3:20][O:19][C:18]1[CH:17]=[CH:16][C:15]([C:23]2[S:24][C:33]3[CH:32]=[C:29]([O:30][CH3:31])[CH:28]=[CH:27][C:26]=3[CH:25]=2)=[CH:22][CH:21]=1

Participants

5

Reactant 3

HCID 24408BromineHCID 521998p-Toluenesulfonic acid monohydrateHCID 10923693HCID 10923693, compound

Product 1

HCID 8509416-Methoxy-2-(4-methoxyphenyl)benzo[b]thiopheneYield 2.5%

Reagents, catalysts & solvents 1

HCID 7964ChlorobenzeneSolvent2×

Procedure

The p-toluene sulfonic acid mono hydrate (310 mg, 1.6 mmol) in 25 ml of chlorobenzene is placed in a 25 ml, 3-neck round bottom flask fitted with a thermometer, nitrogen gas inlet, 10 ml addition funnel, reflux condenser, Dean-Stark trap with drying tube, magnetic stirrer, and heating mantle. 10 ml of solvent is distilled off and bromine (0.08 ml, 1.55 mmol) is added followed by thiodesoxyanisoin (700 mg, 1.6 mmol) in 10 ml of chlorobenzene over 5 minutes. After stirring at reflux for 15 minutes the reaction is allowed to cool to room temperature. A precipitate forms and is filtered off. The filter cake is washed with 50 ml of chlorobenzene. The filtrate is washed with water (2×50 ml), 5% sodium bicarbonate, 50 ml water, and 50 ml of 10% aqueous sodium chloride. The organics are dried over sodium sulfate and concentrated. The crude product is purified by silica gel chromatography then triturated with chlorobenzene. The side product solid is filtered off and the filtrate concentrated. The residue is triturated with ethyl acetate and filtered to give 10.8 mg of pure product. (0.25%). 1H NMR.

Workup

  1. customfitted with a thermometer, nitrogen gas inlet, 10 ml addition funnel
  2. temperaturereflux condenser
  3. customDean-Stark trap with drying tube, magnetic stirrer
  4. temperatureheating mantle
  5. distillation10 ml of solvent is distilled off
  6. temperatureat reflux for 15 minutes the reaction
  7. filtrationA precipitate forms and is filtered off
  8. washThe filter cake is washed with 50 ml of chlorobenzene
  9. washThe filtrate is washed with water (2×50 ml), 5% sodium bicarbonate, 50 ml water, and 50 ml of 10% aqueous sodium chloride
  10. dry with materialThe organics are dried over sodium sulfate
  11. concentrationconcentrated
  12. customThe crude product is purified by silica gel chromatography
  13. customthen triturated with chlorobenzene
  14. filtrationThe side product solid is filtered off
  15. concentrationthe filtrate concentrated
  16. customThe residue is triturated with ethyl acetate
  17. filtrationfiltered

Sources & evidence

ORD record
ord-d8008a663d15449aa776952b818d7d19
Source dataset
uspto-grants-2000_03
Patent number
US06043360

Reaction notes

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