Iodine → HCID 58094757, compound

HRID 2402457Notes

Reaction equation

HRID 2402457 reaction equation
[CH2:1]([N:4]1[CH:8]=[CH:7][N:6]=[C:5]1[C:9]1[S:10][CH:11]=[CH:12][C:13]=1[C:14]1[CH:19]=[CH:18][C:17]([Cl:20])=[CH:16][C:15]=1[Cl:21])[CH:2]=[CH2:3].C([Li])CCC.CCCCCC.[I:33]I>C1COCC1>[CH2:1]([N:4]1[CH:8]=[CH:7][N:6]=[C:5]1[C:9]1[S:10][C:11]([I:33])=[CH:12][C:13]=1[C:14]1[CH:19]=[CH:18][C:17]([Cl:20])=[CH:16][C:15]=1[Cl:21])[CH:2]=[CH2:3]

Participants

6

Reactant 4

HCID 807IodineHCID 8058HexaneHCID 58094849HCID 58094849, compoundHCID 178418339Butyllithium

Product 1

HCID 58094757HCID 58094757, compoundYield 74.7%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a solution of 1-allyl-2-[3-(2,4-dichlorophenyl)-2-thienyl]-1H-imidazole (2.50 g, 7.46 mmol) in THF (80.0 mL) cooled to −78° C. was added dropwise 2.50 M of n-butyllithium in hexane (3.28 mL, 8.20 mmol) and the mixture was stirred for 30 min. To the solution was added dropwise a solution of iodine (2.84 g, 11.2 mmol) in THF (10.0 mL) and the resulting solution was stirred for 15 min at −78° C. The reaction mixture was quenched by addition of saturated sodium bisulfite solution (200 mL) and the resulting mixture was warmed to room temperature while stirring for 30 min. The mixture was extracted with EtOAc (3×250 mL) and the combined organic layers were washed with brine (200 mL). The organic layer was dried over Na2SO4, filtered, and concentrated in vacuo. The residue was purified by column chromatography (SiO2, elution with 1-6% EtOAc in hexane) to give crude product which was further purified by column chromatography (SiO2, elution with 2% MeOH in DCM) to provide 2.57 g of product (71%). LC/MS (FA), ES+ 462. 1H NMR (400 MHz, d6-DMSO) δ: 7.30 (d, J=2.2 Hz, 1H), 7.09 (s, 1H), 6.97 (dd, J=2.2, 8:2 Hz, 1H), 6.75 (d, J=1.3 Hz, 1H), 6.71 (d, J=8.2 Hz, 1H), 6.60 (d, J=1.3 Hz, 1H), 5.10-5.21 (m, 1H), 4.60-4.65 (m, 1H), 4.35-4.41 (m, 1H), 3.80-3.85 (m, 2H).

Workup

  1. stirringthe resulting solution was stirred for 15 min at −78° C
  2. customThe reaction mixture was quenched by addition of saturated sodium bisulfite solution (200 mL)
  3. stirringwhile stirring for 30 min
  4. extractionThe mixture was extracted with EtOAc (3×250 mL)
  5. washthe combined organic layers were washed with brine (200 mL)
  6. dry with materialThe organic layer was dried over Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. customThe residue was purified by column chromatography (SiO2, elution with 1-6% EtOAc in hexane)
  10. customto give crude product which
  11. customwas further purified by column chromatography (SiO2, elution with 2% MeOH in DCM)

Sources & evidence

ORD record
ord-3ae41c8a018d42388041856e53139b0f
Source dataset
uspto-grants-2014_08
Patent number
US08796314B2

Reaction notes

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