Cesium carbonate → HCID 89699797, compound

HRID 1055696Notes

Reaction equation

HRID 1055696 reaction equation
[CH2:1]([O:3][CH:4]([O:17][CH2:18][CH3:19])[CH2:5][N:6]1[C:10]([NH2:11])=[CH:9][C:8]([C:12]2[S:16][CH:15]=[N:14][CH:13]=2)=[N:7]1)[CH3:2].Br[C:21]1[CH:26]=[C:25]([N+:27]([O-:29])=[O:28])[CH:24]=[CH:23][C:22]=1[CH3:30].CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2.C(=O)([O-])[O-].[Cs+].[Cs+]>O1CCOCC1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[CH2:18]([O:17][CH:4]([O:3][CH2:1][CH3:2])[CH2:5][N:6]1[C:10]([NH:11][C:21]2[CH:26]=[C:25]([N+:27]([O-:29])=[O:28])[CH:24]=[CH:23][C:22]=2[CH3:30])=[CH:9][C:8]([C:12]2[S:16][CH:15]=[N:14][CH:13]=2)=[N:7]1)[CH3:19]

Participants

7

Reactant 4

HCID 10796Cesium carbonateHCID 821892-Bromo-4-nitrotolueneHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 89699954HCID 89699954, compound

Product 1

HCID 89699797HCID 89699797, compound

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 312751,4-DioxaneSolvent

Procedure

Under nitrogen, 2.93 g (10.4 mmol) of the compound of Example 81A together with 2.47 g (11.4 mmol) of 2-bromo-4-nitrotoluene, 233 mg (1.04 mmol) of palladium(II) acetate, 901 mg (1.56 mmol) of xantphos [4,5-bis(diphenylphosphino)-9,9-dimethylxanthene] and 10.2 g (31.1 mmol) of caesium carbonate in 43 ml of 1,4-dioxane were heated under reflux for 3 h. After cooling, the mixture was filtered through Celite, the filter cake was washed with ethyl acetate and the filtrate was concentrated under reduced pressure. The crude product obtained in this manner was purified on a Biotage system (100 g Snap column; mobile phase gradient ethyl acetate/0-8% methanol). This gave 3.26 g (75% of theory) of the title compound.

Workup

  1. temperatureunder reflux for 3 h
  2. temperatureAfter cooling
  3. filtrationthe mixture was filtered through Celite
  4. washthe filter cake was washed with ethyl acetate
  5. concentrationthe filtrate was concentrated under reduced pressure

Sources & evidence

ORD record
ord-f329338f9a5d4967b14489ff4b2d4b44
Source dataset
uspto-grants-2016_07
Patent number
US09394309B2

Reaction notes

Loading…