Cesium carbonate → HCID 67026106, compound

HRID 450646Notes

Reaction equation

HRID 450646 reaction equation
Br[C:2]1[CH:3]=[C:4]([C:8]2[O:12][N:11]=[C:10]([C:13]3[CH:14]=[N:15][CH:16]=[CH:17][CH:18]=3)[N:9]=2)[CH:5]=[CH:6][CH:7]=1.[NH:19]1[CH2:23][CH2:22][CH2:21][C:20]1=[O:24].C(=O)([O-])[O-].[Cs+].[Cs+].C1(P(C2C=CC=CC=2)C2C3OC4C(=CC=CC=4P(C4C=CC=CC=4)C4C=CC=CC=4)C(C)(C)C=3C=CC=2)C=CC=CC=1>C1(C)C=CC=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[N:15]1[CH:16]=[CH:17][CH:18]=[C:13]([C:10]2[N:9]=[C:8]([C:4]3[CH:3]=[C:2]([N:19]4[CH2:23][CH2:22][CH2:21][C:20]4=[O:24])[CH:7]=[CH:6][CH:5]=3)[O:12][N:11]=2)[CH:14]=1

Participants

7

Reactant 4

HCID 10796Cesium carbonateHCID 120252-PyrrolidoneHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 878411HCID 878411, compound

Product 1

HCID 67026106HCID 67026106, compound

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolvent

Conditions

Temperature
100 °C

Procedure

A solution of the product of Example 63 (200 mg, 0.66 mmol) and pyrrolidin-2-one (Aldrich, 85 mg, 0.99 mmol) in toluene (anhydrous 10 mL) was degassed and purged with nitrogen three times, cesium carbonate (Aldrich, 324 mg, 0.993 mmol) and tris(dibenzylideneacetone)dipalladium(0) (Aldrich, 12.1 mg, 0.013 mmol), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (Aldrich, 23.0 mg, 0.040 mmol, xantphos) were added, degassed and purged with nitrogen three times. The mixture was then heated to 100° C. and stirred under nitrogen for 15 hours. It was then cooled to ambient temperature and diluted with ethyl acetate (50 mL), washed with brine (2×5 mL), concentrated, purified with chromatography (v. ethyl acetate/hexane=1/1, Rf=0.1) to give the title compound. 1H NMR (300 MHz, DMSO-d6) δ 2.04-2.19 (m, 2 H), 2.57 (t, J=7.9 Hz, 2 H), 3.95 (t, J=6.9 Hz, 2 H), 7.60-7.75 (m, 2 H), 7.84-8.10 (m, 2 H), 8.46 (dt, J=7.9, 2.0 Hz, 1 H), 8.64 (t, J=2.0 Hz, 1 H), 8.82 (dd, J=5.0, 1.8 Hz, 1 H), 9.26 (dd, J=2.4, 0.8 Hz, 1 H) ppm; MS (DCI/NH3) m/z 307 (M+H)+.

Workup

  1. additionwere added
  2. customdegassed
  3. custompurged with nitrogen three times
  4. temperatureIt was then cooled to ambient temperature
  5. additiondiluted with ethyl acetate (50 mL)
  6. washwashed with brine (2×5 mL)
  7. concentrationconcentrated
  8. custompurified with chromatography (v. ethyl acetate/hexane=1/1, Rf=0.1)

Sources & evidence

ORD record
ord-d9adb82dd62548bda3a2ffc775270ac0
Source dataset
uspto-grants-2013_07
Patent number
US08486979B2

Reaction notes

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