Cesium carbonate → HCID 89700178, compound

HRID 1055635Notes

Reaction equation

HRID 1055635 reaction equation
[CH2:1]([O:3][CH:4]([O:23][CH2:24][CH3:25])[CH2:5][N:6]1[C:10]([NH2:11])=[CH:9][C:8]([C:12]2[CH:13]=[N:14][N:15]([CH:17]3[CH2:22][CH2:21][CH2:20][CH2:19][O:18]3)[CH:16]=2)=[N:7]1)[CH3:2].Br[C:27]1[CH:32]=[C:31]([N+:33]([O-:35])=[O:34])[CH:30]=[CH:29][C:28]=1[CH3:36].C(=O)([O-])[O-].[Cs+].[Cs+].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>O1CCOCC1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[CH2:1]([O:3][CH:4]([O:23][CH2:24][CH3:25])[CH2:5][N:6]1[C:10]([NH:11][C:27]2[CH:32]=[C:31]([N+:33]([O-:35])=[O:34])[CH:30]=[CH:29][C:28]=2[CH3:36])=[CH:9][C:8]([C:12]2[CH:13]=[N:14][N:15]([CH:17]3[CH2:22][CH2:21][CH2:20][CH2:19][O:18]3)[CH:16]=2)=[N:7]1)[CH3:2]

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 89700333HCID 89700333, compound

Product 1

HCID 89700178HCID 89700178, compound

Reagents, catalysts & solvents 2

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

Procedure

Under argon, 12.3 g (35.2 mmol) of the compound of Example 1A, 9.9 g (45.8 mmol) of 2-bromo-4-nitrotoluene, 0.79 g (3.52 mmol) of palladium(II) acetate, 22.9 g (70.4 mmol) of caesium carbonate and 2.04 g (3.52 mmol) of xantphos [4,5-bis(diphenylphosphino)-9,9-dimethylxanthene] in 170 ml of 1,4-dioxane were heated at reflux for 4 h. After cooling to RT, the mixture was filtered through kieselguhr and the filtrate was concentrated on a rotary evaporator. The residue was taken up in ethyl acetate and the mixture was washed with semiconcentrated sodium bicarbonate solution and then with concentrated sodium chloride solution. The organic phase was dried over anhydrous sodium sulphate and concentrated. The crude product was purified chromatographically on silica gel (mobile phase gradient dichloromethane/ethyl acetate 2:1→1:3). This gave 15.9 g (92% of theory) of the title compound.

Workup

  1. temperatureat reflux for 4 h
  2. filtrationthe mixture was filtered through kieselguhr
  3. concentrationthe filtrate was concentrated on a rotary evaporator
  4. washthe mixture was washed with semiconcentrated sodium bicarbonate solution
  5. dry with materialThe organic phase was dried over anhydrous sodium sulphate
  6. concentrationconcentrated
  7. customThe crude product was purified chromatographically on silica gel (mobile phase gradient dichloromethane/ethyl acetate 2:1→1:3)

Sources & evidence

ORD record
ord-70fdac76676a4a52a7f11c0baf17fdd5
Source dataset
uspto-grants-2016_07
Patent number
US09394309B2

Reaction notes

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