4-Iodophenol → HCID 89555388, compound

HRID 928642Notes

Reaction equation

HRID 928642 reaction equation
C(=O)([O-])[O-].[K+].[K+].Br[CH2:8][C:9]1[CH:10]=[C:11]([CH:16]=[CH:17][CH:18]=1)[C:12]([O:14]C)=O.[I:19][C:20]1[CH:25]=[CH:24][C:23]([OH:26])=[CH:22][CH:21]=1.[OH-].[Na+].[NH:29]1[CH2:36][CH2:35][CH2:34][C@H:30]1[C:31]([OH:33])=[O:32]>ClCCl.C(OCC)(=O)C.CO.C1COCC1.CN(C=O)C>[I:19][C:20]1[CH:25]=[CH:24][C:23]([O:26][CH2:8][C:9]2[CH:10]=[C:11]([CH:16]=[CH:17][CH:18]=2)[C:12]([N:29]2[CH2:36][CH2:35][CH2:34][C@H:30]2[C:31]([OH:33])=[O:32])=[O:14])=[CH:22][CH:21]=1

Participants

11

Reactant 5

HCID 108944-IodophenolHCID 11430Potassium CarbonateHCID 14798Sodium Hydroxide2×HCID 145742L-ProlineHCID 517981Methyl 3-(bromomethyl)benzoate

Product 1

HCID 89555388HCID 89555388, compoundYield 64%

Reagents, catalysts & solvents 5

HCID 887MethanolSolventHCID 6228DimethylformamideSolvent2×HCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent2×HCID 8857Ethyl AcetateSolvent2×

Procedure

N,N-dimethylformamide (hereinafter, DMF) (100 mL), potassium carbonate (1.1 g, 7.8 mmol), and methyl 3-(bromomethyl)benzoate (1.2 g, 5.2 mmol) were added to 4-iodophenol (1.2 g, 5.5 mmol), and stirred at room temperature overnight. Ethyl acetate was used as an extraction solvent, and after washing with water, a 1 N sodium hydroxide aqueous solution, and saturated brine, the resultant was dried over magnesium sulfate. The solvent was distilled away under reduced pressure. To the resulting residue (1.9 g, 5.2 mmol), tetrahydrofuran (hereinafter, THF) (10 mL), methanol (10 mL), and a 1 N sodium hydroxide aqueous solution (20 mL) were added, and stirred at room temperature for 4 hours. Ethyl acetate was used as an extraction solvent, and after washing with a 1 N hydrochloric acid aqueous solution and saturated brine, the resultant was dried over magnesium sulfate. The solvent was distilled away under reduced pressure. To the resulting residue, thionyl chloride (20 mL) was added, and stirred at 40° C. for 1 hour. After that, the solvent was distilled away under reduced pressure. To the resulting residue, dichloromethane (10 mL), a 1 N sodium hydroxide aqueous solution (15 mL), and L-proline (1.1 g, 9.2 mmol) were added, and stirred at room temperature overnight. The solvent was distilled away under reduced pressure. The resultant was washed with a 1 N hydrochloric acid aqueous solution and saturated brine, and then dried over magnesium sulfate. The solvent was distilled away under reduced pressure. The resulting residue was washed with a water-acetonitrile mixture solvent, and then dried to thus obtain the title compound.

Workup

  1. washafter washing with water
  2. dry with materiala 1 N sodium hydroxide aqueous solution, and saturated brine, the resultant was dried over magnesium sulfate
  3. distillationThe solvent was distilled away under reduced pressure
  4. stirringstirred at room temperature for 4 hours
  5. washafter washing with a 1 N hydrochloric acid aqueous solution and saturated brine
  6. dry with materialthe resultant was dried over magnesium sulfate
  7. distillationThe solvent was distilled away under reduced pressure
  8. additionTo the resulting residue, thionyl chloride (20 mL) was added
  9. stirringstirred at 40° C. for 1 hour
  10. distillationAfter that, the solvent was distilled away under reduced pressure
  11. stirringstirred at room temperature overnight
  12. distillationThe solvent was distilled away under reduced pressure
  13. washThe resultant was washed with a 1 N hydrochloric acid aqueous solution and saturated brine
  14. dry with materialdried over magnesium sulfate
  15. distillationThe solvent was distilled away under reduced pressure
  16. washThe resulting residue was washed with a water-acetonitrile mixture solvent
  17. customdried

Sources & evidence

ORD record
ord-465f551b95934dd39b1a1ee9e30533da
Source dataset
uspto-grants-2016_03
Patent number
US09290487B2

Reaction notes

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