1-Bromo-2-chloro-4-iodobenzene → 2-(4-Bromo-3-chlorophenyl)thiophene

HRID 409362Notes

Reaction equation

HRID 409362 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5](I)=[CH:4][C:3]=1[Cl:9].C([Sn](CCCC)(CCCC)[C:15]1[S:16][CH:17]=[CH:18][CH:19]=1)CCC.CCOC(C)=O.CCCCCC>O1CCOCC1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([C:15]2[S:16][CH:17]=[CH:18][CH:19]=2)=[CH:4][C:3]=1[Cl:9]

Participants

6

Reactant 3

HCID 27568861-Bromo-2-chloro-4-iodobenzeneHCID 27793732-(Tri-n-butylstannyl)thiopheneHCID 21226206Ethyl acetate hexane

Product 1

HCID 579940542-(4-Bromo-3-chlorophenyl)thiophene

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 312751,4-DioxaneSolvent

Procedure

To a mixture of 1-bromo-2-chloro-4-iodobenzene (2.0 g, 6.30 mmol) in dioxane 30 mL, 2-tributylstannyl thiophene (2.352 g, 6.30 mmol), and 5% equivalent of Pd(PPh3)4 (0.364 g, 0.3155 mmol) is refluxed under nitrogen for 5 h. After cooling and evaporation of the solvent, the residue is dissolved in EtOAc 50 mL. 10% KF 30 mL is added and the solution is stirred at r.t. for 30 min. The resultant precipitate is removed by filtration. The solution is washed with water 20 mL×3, and dried with Na2SO4 and concentrated. The pure product (1.2 g, 4.39 mmol, white solid) is obtained by column chromatography using EtOAc/Hexane, 1-3% ration solvent system. 1H-NMR (CDCl3/300 MHz): 7.74 (d, J=2.1 Hz, 1H), 7.65 (d, J=7.2 Hz, 1H), 7.37 (m, 3H), 7.14 (m, 1H). MS (ES−, m/z): 529.2 (M+−Br, 20.0).

Workup

  1. temperatureis refluxed under nitrogen for 5 h
  2. temperatureAfter cooling
  3. customevaporation of the solvent
  4. dissolutionthe residue is dissolved in EtOAc 50 mL
  5. addition10% KF 30 mL is added
  6. customThe resultant precipitate is removed by filtration
  7. washThe solution is washed with water 20 mL×3
  8. dry with materialdried with Na2SO4
  9. concentrationconcentrated
  10. customThe pure product (1.2 g, 4.39 mmol, white solid) is obtained by column chromatography

Sources & evidence

ORD record
ord-01825ac4a1b8463888a3bdc7b1eec4e0
Source dataset
uspto-grants-2014_06
Patent number
US08759384B2

Reaction notes

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