Cesium carbonate → HCID 66755610, compound

HRID 1177360Notes

Reaction equation

HRID 1177360 reaction equation
[CH2:1]([C:4]1[C:13]([OH:14])=[CH:12][C:7]([C:8]([O:10][CH3:11])=[O:9])=[CH:6][C:5]=1[C:15]([O:17][CH3:18])=[O:16])[CH:2]=[CH2:3].[CH3:19][S:20]([C:23]1[CH:28]=[CH:27][C:26](F)=[CH:25][CH:24]=1)(=[O:22])=[O:21].C([O-])([O-])=O.[Cs+].[Cs+]>CN(C=O)C.[Cu]I>[CH2:1]([C:4]1[C:13]([O:14][C:26]2[CH:27]=[CH:28][C:23]([S:20]([CH3:19])(=[O:22])=[O:21])=[CH:24][CH:25]=2)=[CH:12][C:7]([C:8]([O:10][CH3:11])=[O:9])=[CH:6][C:5]=1[C:15]([O:17][CH3:18])=[O:16])[CH:2]=[CH2:3]

Participants

6

Reactant 3

HCID 10796Cesium carbonateHCID 679941-Fluoro-4-(methylsulphonyl)benzeneHCID 11791598Dimethyl 4-allyl-5-hydroxyisophthalate

Product 1

HCID 66755610HCID 66755610, compoundYield 78%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
100 °C

Procedure

A mixture of dimethyl 4-allyl-5-hydroxyisophthalate (2.0 g, 7.99 mmol), 4-fluorophenyl methyl sulfone (2.1 g, 12 mmol), Cs2CO3 (5.2 g, 16 mmol) and CuI (400 mg, 2.1 mmol) in DMF (20 mL) was heated to 100° C. for 4 hours. The solvent was removed under reduced pressure. The residue was poured into water (20 mL) and extracted with EtOAc (50 mL×2). The combined organic layer was washed with brine (20 mL×2), dried over Na2SO4 and concentrated. The product was purified via silica gel gradient chromatography eluted with EtOAc in hexanes (10/90 to 30/90) to afford the title compound (2.5 g, 78%) as a white solid. 1H NMR (300 MHz, CHLOROFORM-d) δ ppm 1.83 (dd, J=6.69, 1.60 Hz, 2 H) 3.03-3.16 (m, 3 H) 3.93 (d, 6 H) 6.14-6.34 (m, 1 H) 6.63 (dd, J=16.11, 1.60 Hz, 1 H) 6.88-6.98 (m, 1 H) 6.97-7.09 (m, 2 H) 7.79 (d, J=1.70 Hz, 1 H) 7.87-8.01 (m, 2 H) 8.29 (d, J=1.70 Hz, 1 H); LC-MS (ESI)+m/z=405.00 (M+H)+.

Workup

  1. customThe solvent was removed under reduced pressure
  2. additionThe residue was poured into water (20 mL)
  3. extractionextracted with EtOAc (50 mL×2)
  4. washThe combined organic layer was washed with brine (20 mL×2)
  5. dry with materialdried over Na2SO4
  6. concentrationconcentrated
  7. customThe product was purified via silica gel gradient chromatography
  8. washeluted with EtOAc in hexanes (10/90 to 30/90)

Sources & evidence

ORD record
ord-41b3fa8c47524aae96855b5a1c4fd992
Source dataset
uspto-grants-2010_11
Patent number
US07842713B2

Reaction notes

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