Cesium carbonate → HCID 117746867, compound

HRID 1504477Notes

Reaction equation

HRID 1504477 reaction equation
[NH2:1][C:2]1[CH:7]=[CH:6][C:5]([S:8][CH2:9][C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=2)=[CH:4][C:3]=1/[CH:16]=[CH:17]/[C:18]([O:20][CH2:21][CH3:22])=[O:19].[Br:23][C:24]1[CH:31]=[C:30]([O:32][CH3:33])[C:29](I)=[CH:28][C:25]=1[C:26]#[N:27].C(=O)([O-])[O-].[Cs+].[Cs+]>CCOC(C)=O.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].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>[CH2:9]([S:8][C:5]1[CH:6]=[CH:7][C:2]([NH:1][C:29]2[CH:28]=[C:25]([C:26]#[N:27])[C:24]([Br:23])=[CH:31][C:30]=2[O:32][CH3:33])=[C:3](/[CH:16]=[CH:17]/[C:18]([O:20][CH2:21][CH3:22])=[O:19])[CH:4]=1)[C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1

Participants

7

Reactant 3

HCID 10796Cesium carbonateHCID 117737295HCID 117737295, compoundHCID 117740420(E)-Ethyl 3-(2-amino-5-(benzylthio)phenyl)acrylate

Product 1

HCID 117746867HCID 117746867, compoundYield 92.3%

Reagents, catalysts & solvents 3

HCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)CatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
110 °C

Procedure

A RBF was charged with (E)-ethyl 3-(2-amino-5-(benzylthio)phenyl)acrylate (625 mg, 1.994 mmol, made via Method 42, Steps 1-2), 2-bromo-5-iodo-4-methoxybenzonitrile (809 mg, 2.393 mmol), Xantphos (57.7 mg, 0.100 mmol), Pd2(dba)3 (45.7 mg, 0.050 mmol), and cesium carbonate (1624 mg, 4.99 mmol) were added. A reflux condenser was attached, and the flask was heated to 110° C. overnight. The mixture was cooled, diluted with EtOAc, and filtered through celite with the aid of EtOAc. The filtrate was concentrated. The residue was taken up in 2-PrOH, and the mixture was heated to boiling briefly then sonicated for 30 s. When the mixture had returned to room temperature, it was filtered; and the filtered solid was washed with 2-PrOH (3×). The collected solid was dried on the filter under a flow of N2 (g) for 15 min to give (E)-ethyl 3-(5-(benzylthio)-2-((4-bromo-5-cyano-2-methoxyphenyl)amino)phenyl)acrylate (963 mg, 1.840 mmol, 92% yield) as a bright-yellow solid. m/z (ESI) 545.0 (M+Na)+.

Workup

  1. additionwere added
  2. customA reflux condenser was attached
  3. temperatureThe mixture was cooled
  4. filtrationfiltered through celite with the aid of EtOAc
  5. concentrationThe filtrate was concentrated
  6. temperaturethe mixture was heated
  7. customto boiling briefly then sonicated for 30 s
  8. customhad returned to room temperature
  9. filtrationit was filtered
  10. washand the filtered solid was washed with 2-PrOH (3×)
  11. customThe collected solid was dried on the
  12. filtrationfilter under a flow of N2 (g) for 15 min

Sources & evidence

ORD record
ord-a525e56c11ff488dac9e3abbeef5ac2e
Source dataset
uspto-grants-2015_12
Patent number
US09212182B2

Reaction notes

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