Potassium Carbonate → 1-Iodo-4-(2-methyl-3-butyn-2-yloxy)-2-nitrobenzene

HRID 600378Notes

Reaction equation

HRID 600378 reaction equation
Cl[C:2]([CH3:6])([CH3:5])[C:3]#[CH:4].[I:7][C:8]1[CH:13]=[CH:12][C:11]([OH:14])=[CH:10][C:9]=1[N+:15]([O-:17])=[O:16].C(=O)([O-])[O-].[K+].[K+]>[I-].C([N+](CCCC)(CCCC)CCCC)CCC.CC(C)=O.C(OCC)(=O)C>[I:7][C:8]1[CH:13]=[CH:12][C:11]([O:14][C:2]([CH3:6])([C:3]#[CH:4])[CH3:5])=[CH:10][C:9]=1[N+:15]([O-:17])=[O:16]

Participants

7

Reactant 3

HCID 11430Potassium CarbonateHCID 706791-Butyne, 3-chloro-3-methyl-HCID 27334544-Iodo-3-nitrophenol

Product 1

HCID 577342961-Iodo-4-(2-methyl-3-butyn-2-yloxy)-2-nitrobenzeneYield 91%

Reagents, catalysts & solvents 3

HCID 67553Tetrabutylammonium IodideCatalystHCID 180AcetoneSolventHCID 8857Ethyl AcetateSolvent2×

Conditions

Temperature
65 °C

Procedure

3-Chloro-3-methyl-1-butyne (640 μL, 5.7 mmol, 3.0 equiv) was added to a stirred solution of 4-iodo-3-nitrophenol (500 mg, 1.89 mmol, 1 equiv), tetrabutylammonium iodide (2.10 g, 5.7 mmol, 3.0 equiv), and potassium carbonate (522 mg, 3.8 mmol, 2.0 equiv) in acetone (5.2 mL) at 23° C. The reaction mixture was warmed to 65° C. and was heated at this temperature for 18 h. The product solution was allowed to cool to 23° C., then was diluted with ethyl acetate (50 mL). The diluted product solution was washed with saturated aqueous sodium bicarbonate solution (5 mL) and saturated aqueous sodium chloride solution (5 mL). After washing, the organic layer was dried over sodium sulfate and the solids were filtered. The filtrate was concentrated. The residue obtained was dissolved in ethyl acetate (10 mL) and the resulting solution was filtered through a pad of Celite, eluting with ethyl acetate (50 mL). The eluent was concentrated and the residue obtained was purified by flash-column chromatography (4% acetone-hexanes) to furnish 1-iodo-4-(2-methyl-3-butyn-2-yloxy)-2-nitrobenzene as a pale yellow oil (569 mg, 91%).

Workup

  1. temperaturewas heated at this temperature for 18 h
  2. temperatureto cool to 23° C.
  3. washThe diluted product solution was washed with saturated aqueous sodium bicarbonate solution (5 mL) and saturated aqueous sodium chloride solution (5 mL)
  4. washAfter washing
  5. dry with materialthe organic layer was dried over sodium sulfate
  6. filtrationthe solids were filtered
  7. concentrationThe filtrate was concentrated
  8. customThe residue obtained
  9. filtrationthe resulting solution was filtered through a pad of Celite
  10. washeluting with ethyl acetate (50 mL)
  11. concentrationThe eluent was concentrated
  12. customthe residue obtained
  13. customwas purified by flash-column chromatography (4% acetone-hexanes)

Sources & evidence

ORD record
ord-a7d6f68955ac413dbf6299e5dc7f5a6b
Source dataset
uspto-grants-2011_03
Patent number
US07902196B2

Reaction notes

Loading…