Cesium carbonate → Tert-butyl 2-[(4-{[4-(dimethylamino)phenyl]ethynyl}phenyl)acetyl]hydrazinecarboxylate

HRID 1465440Notes

Reaction equation

HRID 1465440 reaction equation
Br[C:2]1[CH:10]=[CH:9][C:5]([N:6]([CH3:8])[CH3:7])=[CH:4][CH:3]=1.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.[C:59]([C:61]1[CH:66]=[CH:65][C:64]([CH2:67][C:68]([NH:70][NH:71][C:72]([O:74][C:75]([CH3:78])([CH3:77])[CH3:76])=[O:73])=[O:69])=[CH:63][CH:62]=1)#[CH:60]>C(#N)C.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[CH3:7][N:6]([CH3:8])[C:5]1[CH:9]=[CH:10][C:2]([C:60]#[C:59][C:61]2[CH:62]=[CH:63][C:64]([CH2:67][C:68]([NH:70][NH:71][C:72]([O:74][C:75]([CH3:78])([CH3:77])[CH3:76])=[O:73])=[O:69])=[CH:65][CH:66]=2)=[CH:3][CH:4]=1

Participants

7

Reactant 4

HCID 10796Cesium carbonateHCID 114654-bromo-N,N-dimethylanilineHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 86651837Tert-butyl 2-[(4-ethynylphenyl)acetyl]hydrazinecarboxylate

Product 1

HCID 58181354Tert-butyl 2-[(4-{[4-(dimethylamino)phenyl]ethynyl}phenyl)acetyl]hydrazinecarboxylateYield 38.3%

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalystHCID 6342AcetonitrileSolvent2×

Procedure

To a mixture of 4-bromo-N,N-dimethylaniline (175 mg, 0.88 mmol), cesium carbonate (476 mg, 1.46 mmol), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (22 mg, 0.04 mmol) and bis(acetonitrile)dichloropalladium (II) (10 mg, 0.04 mmol) was added anhydrous acetonitrile (2 ml), and the mixture was stirred at room temperature for 15 mins. A solution of tert-butyl 2-[(4-ethynylphenyl)acetyl]hydrazinecarboxylate (200 mg, 0.73 mmol) in anhydrous acetonitrile (4 ml) was added, and the mixture was stirred at 80° C. for 5 hrs. After cooling, the reaction mixture was filtered, and the insoluble material was washed with ethyl acetate. The filtrate and washing solution were combined and concentrated under reduced pressure. The concentrated residue was purified by silica gel column chromatography (chloroform:methanol=97:3) to give tert-butyl 2-[(4-{[4-(dimethylamino)phenyl]ethynyl}phenyl)acetyl]hydrazinecarboxylate (110 mg, yield 38%) as a yellow solid.

Workup

  1. stirringthe mixture was stirred at 80° C. for 5 hrs
  2. temperatureAfter cooling
  3. filtrationthe reaction mixture was filtered
  4. washthe insoluble material was washed with ethyl acetate
  5. washThe filtrate and washing solution
  6. concentrationconcentrated under reduced pressure
  7. customThe concentrated residue was purified by silica gel column chromatography (chloroform:methanol=97:3)

Sources & evidence

ORD record
ord-4f5454c0934b4e60b06dbdc03116b095
Source dataset
uspto-grants-2015_04
Patent number
US08999989B2

Reaction notes

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