Cesium carbonate → HCID 21069896, compound

HRID 1664160Notes

Reaction equation

HRID 1664160 reaction equation
Br[C:2]1[CH:9]=[C:8]([F:10])[CH:7]=[CH:6][C:3]=1[C:4]#[N:5].[NH:11]1[CH2:15][CH2:14][CH2:13][C:12]1=[O:16].C([O-])([O-])=O.[Cs+].[Cs+]>O1CCOCC1.CC1(C)C2C=CC=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=2OC2C1=CC=CC=2P(C1C=CC=CC=1)C1C=CC=CC=1>[F:10][C:8]1[CH:7]=[CH:6][C:3]([C:4]#[N:5])=[C:2]([N:11]2[CH2:15][CH2:14][CH2:13][C:12]2=[O:16])[CH:9]=1

Participants

6

Reactant 3

HCID 10796Cesium carbonateHCID 120252-PyrrolidoneHCID 1189392-Bromo-4-fluorobenzonitrile

Product 1

HCID 21069896HCID 21069896, compoundYield 87%

Reagents, catalysts & solvents 2

HCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)CatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
105 °C

Procedure

A 48 mL pressure vessel containing 2-bromo-4-fluorobenzonitrile (1.00 g, 5.00 mmol), 2-pyrrolidinone (0.46 mL, 6.00 mmol), Cs2CO3 (2.28 g, 7.0 mmol) and 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene (xantphos) (0.231 g, 0.40 mmol) in dioxane (6 mL) was degassed with argon for 15 min. Pd2dba3 was introduced and the reaction mixture heated at 105° C. for 48 h. The mixture was cooled, diluted with ethyl acetate or dioxane, and then filtered through Celite®. The resulting mixture was concentrated in vacuo and subjected to column chromatography on silica gel with hexanes:ethyl acetate (3:7) gradient as the eluent to afford the title compound as a white solid (0.887 g, 87% yield): 1H NMR (400 MHz, CDCl3) δ ppm: 7.69 (1H, dd, J=5.8, 8.6 Hz), 7.22 (1H, dd, J=2.5, 9.6 Hz), 7.07 (1H, ddd, J=2.5, 7.6, 8.6 Hz), 3.96 (2H, t, J=7.0 Hz), 2.62 (2H, t, J=8.1 Hz), 2.30-2.22 (2H, m); LCMS (+ESI, M+H+) m/z 205.

Workup

  1. customwas degassed with argon for 15 min
  2. additionPd2dba3 was introduced
  3. temperatureThe mixture was cooled
  4. additiondiluted with ethyl acetate or dioxane
  5. filtrationfiltered through Celite®
  6. concentrationThe resulting mixture was concentrated in vacuo

Sources & evidence

ORD record
ord-1c2b94dafb2c4aaaa1b76a2da81763cb
Source dataset
uspto-grants-2011_10
Patent number
US08039458B2

Reaction notes

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