Cesium carbonate → HCID 66599396, compound

HRID 2410697Notes

Reaction equation

HRID 2410697 reaction equation
[NH2:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH:13]=[CH:12][CH:11]=[C:10]([O:14][CH3:15])[CH:9]=2)=[CH:4][C:3]=1[C:16]#[N:17].Br[C:19]1[CH:20]=[C:21]([CH:26]=[CH:27][CH:28]=1)[C:22]([O:24][CH3:25])=[O:23].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.C(=O)([O-])[O-].[Cs+].[Cs+]>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1(C)C=CC=CC=1>[C:16]([C:3]1[CH:4]=[C:5]([C:8]2[CH:13]=[CH:12][CH:11]=[C:10]([O:14][CH3:15])[CH:9]=2)[CH:6]=[CH:7][C:2]=1[NH:1][C:19]1[CH:20]=[C:21]([CH:26]=[CH:27][CH:28]=1)[C:22]([O:24][CH3:25])=[O:23])#[N:17]

Participants

7

Reactant 4

HCID 10796Cesium carbonateHCID 12070Methyl 3-bromobenzoateHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 66599222HCID 66599222, compound

Product 1

HCID 66599396HCID 66599396, compoundYield 76%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 1140TolueneSolvent

Conditions

Temperature
100 °C

Procedure

4-Amino-3′-methoxybiphenyl-3-carbonitrile (4.23 g, 18.86 mmol), methyl 3-bromobenzoate (4.87 g, 22.63 mmol), palladium(II) acetate (0.212 g, 0.943 mmol), 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene (1.091 g, 1.886 mmol) and cesium carbonate (8.60 g, 26.4 mmol) in a pressure vessel was flushed with nitrogen and toluene (75 mL) was added. The mixture was heated at 100° C. overnight. The reaction mixture was filtered and the solid was washed with DCM (2×20 mL). The filtrate was concentrated and the product was purified by flash-chromatography eluting with hexane containing 5 to 20% ethyl acetate. This gave 5.14 g (65% yield) of methyl 3-(3-cyano-3′-methoxybiphenyl-4-ylamino)benzoate. MS (ESI) m/z 359.1 (M+H). 1H NMR (CDCl3) δ ppm 7.88 (1H, s), 7.77 (1H, d, J=7.63 Hz), 7.72 (1H, d, J=2.44 Hz), 7.61 (1H, dd, J=8.70, 2.29 Hz), 7.42 (1H, t, J=7.93 Hz), 7.30-7.39 (2H, m), 7.27 (1H, d, J=8.85 Hz), 7.08 (1H, d, J=7.93 Hz), 7.02 (1H, t, J=2.14 Hz), 6.88 (1H, dd, J=8.24, 2.44 Hz), 6.56 (1H, s), 3.91 (3H, s), 3.85 (3H, s).

Workup

  1. additionwas added
  2. filtrationThe reaction mixture was filtered
  3. washthe solid was washed with DCM (2×20 mL)
  4. concentrationThe filtrate was concentrated
  5. customthe product was purified by flash-chromatography
  6. washeluting with hexane containing 5 to 20% ethyl acetate

Sources & evidence

ORD record
ord-bb929ea582504ccf82c114576d067d58
Source dataset
uspto-grants-2014_08
Patent number
US08815840B2

Reaction notes

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