Cesium carbonate → HCID 66933906, compound

HRID 1879565Notes

Reaction equation

HRID 1879565 reaction equation
C1C=CC(P(C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[N+:47]([C:50]1[CH:55]=[CH:54][C:53](I)=[CH:52][CH:51]=1)([O-:49])=[O:48].Cl.[CH2:58]([O:65][C:66]1[CH:72]=[CH:71][C:69]([NH2:70])=[CH:68][CH:67]=1)[C:59]1[CH:64]=[CH:63][CH:62]=[CH:61][CH:60]=1.C([O-])([O-])=O.[Cs+].[Cs+]>CC([O-])=O.CC([O-])=O.[Pd+2].O.C1(C)C=CC=CC=1>[CH2:58]([O:65][C:66]1[CH:67]=[CH:68][C:69]([NH:70][C:53]2[CH:54]=[CH:55][C:50]([N+:47]([O-:49])=[O:48])=[CH:51][CH:52]=2)=[CH:71][CH:72]=1)[C:59]1[CH:60]=[CH:61][CH:62]=[CH:63][CH:64]=1

Participants

8

Reactant 4

HCID 10796Cesium carbonateHCID 124951-Iodo-4-nitrobenzeneHCID 634876Binap, (A+-)-HCID 27238314-Benzyloxyaniline hydrochloride

Product 1

HCID 66933906HCID 66933906, compoundYield 31.2%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 962WaterSolventHCID 1140TolueneSolvent2×

Procedure

To a oven dried flask was charged with Pd(OAc)2 (81 mg, 0.36 mmol) and (S)-(−)-BINAP (336 mg, 0.54 mmol), followed by toluene (10 mL). The mixture was stirred under Ar at room temperature for 5 min. To this mixture was added 4-nitroiodobenzene (3.0 g, 12 mmol), 4-benzyloxyaniline hydrochloride (3.39 g, 14.4 mmol), Cs2CO3 (9.8 g, 30 mmol) and toluene (40 mL). The resulting mixture was heated under Ar at 100° C. for 16 hrs, and then cooled to room temperature and poured into H2O (100 mL). The layers were separated. The aqueous layer was extracted with EtOAc (3×20 mL). The combined organic layers were washed with brine (2×20 mL), dried (MgSO4) and filtered. The filtrate was concentrated. The residue was purified via column chromatography (silica gel, 5-40% EtOAc/hexane) to give the desired product as an orange solid (1.2 g, 31%). 1H NMR (CDCl3, 400 MHz) δ: 8.09 (d, J=9.2 Hz, 2H), 7.30-7.49 (m, 5H), 7.15 (d, J=9.2 Hz, 2H), 7.01 (d, J=9.2 Hz, 2H), 6.77 (d, J=8.8 Hz, 2H), 6.10 (br s, 1H), 5.09 (s, 2H). MS: m/z=321 (M+H+)+.

Workup

  1. customTo a oven dried flask
  2. temperatureThe resulting mixture was heated under Ar at 100° C. for 16 hrs
  3. temperaturecooled to room temperature
  4. customThe layers were separated
  5. extractionThe aqueous layer was extracted with EtOAc (3×20 mL)
  6. washThe combined organic layers were washed with brine (2×20 mL)
  7. dry with materialdried (MgSO4)
  8. filtrationfiltered
  9. concentrationThe filtrate was concentrated
  10. customThe residue was purified via column chromatography (silica gel, 5-40% EtOAc/hexane)

Sources & evidence

ORD record
ord-1a638057f314400d8ffc9181f1aba781
Source dataset
uspto-grants-2012_11
Patent number
US08318132B2

Reaction notes

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