Bromine → HCID 59769746, compound

HRID 2220321Notes

Reaction equation

HRID 2220321 reaction equation
[Br:1]Br.[F:3][CH:4]1[CH2:12][CH2:11][C:7]2[S:8][CH:9]=[CH:10][C:6]=2[C:5]1=[O:13].S([O-])([O-])(=O)=S.[Na+].[Na+]>C(Cl)(Cl)(Cl)Cl.C(OCC)C>[Br:1][C:4]1([F:3])[CH2:12][CH2:11][C:7]2[S:8][CH:9]=[CH:10][C:6]=2[C:5]1=[O:13]

Participants

6

Reactant 3

HCID 24408Bromine3×HCID 24477Sodium ThiosulfateHCID 21636547HCID 21636547, compound

Product 1

HCID 59769746HCID 59769746, compoundYield 49%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 5943Carbon TetrachlorideSolvent

Procedure

Add a solution of bromine (10.08 g, 63.1 mmol, 1.1 equiv.) in dry carbon tetrachloride (60 mL) dropwise via addition funnel over 1 h20 min to a cold (0° C.) solution of 5-fluoro-6,7-dihydro-5H-benzo[b]thiophen-4-one (9.72 g, 57.1 mmol, 1 equiv.) in dry diethyl ether (300 mL). Once all the bromine is added warm to room temperature for 2 hours and add more bromine (0.7 M in CCl4, 7 mL, 4.9 mmol, 0.09 equiv.) and stir the reaction mixture at room temperature for 1 hr before adding saturated aqueous sodium thiosulfate. The layers are separated and the aqueous layer is extracted with diethyl ether (three times). The combined organic extracts are dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. Purify the resultant crude material by medium pressure liquid chromatography eluting with 0 to 20% ethyl acetate in hexanes to afford the title compound (6.976 g, 49%). δH (400 MHz, CDCl3) 2.67-2.78 (m, 1H), 2.93 (dddd, 1H, J=14, 4, 4, 4 Hz), 3.24-3.31 (m, 2H), 7.21 (d, 1H, J=6 Hz), 7.45 (d, 1H, J=6 Hz).

Workup

  1. customThe layers are separated
  2. extractionthe aqueous layer is extracted with diethyl ether (three times)
  3. dry with materialThe combined organic extracts are dried over anhydrous magnesium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated under reduced pressure
  6. customPurify the resultant crude material by medium pressure liquid chromatography
  7. washeluting with 0 to 20% ethyl acetate in hexanes

Sources & evidence

ORD record
ord-38099a21be0945beb6a0251d08f0fe24
Source dataset
uspto-grants-2008_08
Patent number
US07417064B2

Reaction notes

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