Triethylamine → HCID 54500120, compound

HRID 1636509Notes

Reaction equation

HRID 1636509 reaction equation
I[C:2]1[C:7]2[O:8][C:9]3[C:14]([Si:15]([CH3:18])([CH3:17])[CH3:16])=[CH:13][CH:12]=[CH:11][C:10]=3[C:6]=2[CH:5]=[CH:4][CH:3]=1.C(N(CC)CC)C.[C:26]([O:30][CH2:31][CH3:32])(=[O:29])[CH:27]=[CH2:28]>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.[Pd].C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.C(#N)C>[CH2:31]([O:30][C:26](=[O:29])[CH:27]=[CH:28][C:2]1[C:7]2[O:8][C:9]3[C:14]([Si:15]([CH3:18])([CH3:17])[CH3:16])=[CH:13][CH:12]=[CH:11][C:10]=3[C:6]=2[CH:5]=[CH:4][CH:3]=1)[CH3:32]

Participants

8

Reactant 3

HCID 8471TriethylamineHCID 8821Ethyl AcrylateHCID 10737601HCID 10737601, compound

Product 1

HCID 54500120HCID 54500120, compoundYield 93%

Reagents, catalysts & solvents 4

HCID 23938PalladiumCatalystHCID 80271Tri-o-tolylphosphineCatalystHCID 167845palladium(II) acetateCatalystHCID 6342AcetonitrileSolvent

Procedure

An oven-dried, 100 mL round-bottomed flask was cooled under Ar and charged with 4-iodo-6-trimethylsilyldibenzofuran (5) (3.82 g, 10.4 mmol), palladium acetate (49.2 mg, 2.1 mol %), and tri-ortho-tolylphosphine (0.162 g, 5.1 mol %). The flask was fitted with a condenser and the system was alternately evacuated under high vacuum and flushed with Ar (4 cycles). Acetonitrile (16.5 mL), triethylamine (4.36 mL, 31.1 mmol), and ethyl acrylate (3.39 mL, 31.3 mmol) were added through the condenser and the mixture was heated to 85÷C in an oil bath. The reaction mixture was cooled to room temperature when the palladium precipitated after 2 hours. The mixture was concentrated under reduced pressure to give a yellow-brown solid which was then partitioned between CH2Cl2 (120 mL) and H2O (150 mL). The aqueous layer was extracted with CH2Cl2 (3×75 mL). The combined organic layers were dried over MgSO4 and concentrated under reduced pressure. The crude material was purified by flash chromatography (95:5 hexanes:ethyl acetate) to afford the pure compound (3.27 g, 93%) as an oil which solidified upon standing to afford beige solid: mp 48-52° C.; 1H NMR (d6-acetone) d 8.16 (d, Jo=7.6, 2H, Ar H1 and H9), 7.98 (d, J=16.2, 1H, --CHCHCO2Et), 7.77 (dd, Jo=7.0, Jp=0.6, 1H, Ar H3), 7.64 (dd, Jo=7.2, Jm=1.3, 1H, Ar H7), 7.44 (td, Jo=7.6, Jm=1.6, 2H, Ar H2 and H8), 7.20 (d, J=16.2, 1H, --CHCHCO2Et), 4.28 (q, J=7.1, 2H, --CO2CH2CH3), 1.34 (t, J=7.1, 3H, --CO2CH2CH3), 0.52 (s, 8H, --Si(CH3)3); 13C NMR (d6-acetone) d 167.51, 139.99, 134.60, 134.32, 129.78, 126.14, 124.59, 124.55, 124.08, 123.89, 123.36, 123.25, 122.98, 120.74, 61.27, 14.99, -0.56; EIMS m/z 338.1349, M+ calcd for C20H22O3Si 338.1338.

Workup

  1. temperatureAn oven-dried, 100 mL round-bottomed flask was cooled under Ar
  2. customThe flask was fitted with a condenser
  3. customthe system was alternately evacuated under high vacuum
  4. customflushed with Ar (4 cycles)
  5. temperaturethe mixture was heated to 85÷C in an oil bath
  6. customprecipitated after 2 hours
  7. concentrationThe mixture was concentrated under reduced pressure
  8. customto give a yellow-brown solid which
  9. customwas then partitioned between CH2Cl2 (120 mL) and H2O (150 mL)
  10. extractionThe aqueous layer was extracted with CH2Cl2 (3×75 mL)
  11. dry with materialThe combined organic layers were dried over MgSO4
  12. concentrationconcentrated under reduced pressure
  13. customThe crude material was purified by flash chromatography (95:5 hexanes:ethyl acetate)

Sources & evidence

ORD record
ord-ba864229057c4b16be1bf3a8df493afb
Source dataset
uspto-grants-2000_03
Patent number
US06034211

Reaction notes

Loading…