Cesium carbonate → 3-Methoxyaniline

HRID 1481667Notes

Reaction equation

HRID 1481667 reaction equation
C(OC(=O)[NH:7][C:8]1[CH:13]=[CH:12][CH:11]=[C:10]([O:14][C:15]2C(C(=O)NC3C=CC=CC=3)=CN=C(SC)N=2)[CH:9]=1)(C)(C)C.C(OC(=O)NC1C=CC=C(OC2C(C(=O)NC3C=CC=CC=3)=CN=C(S(C)(=O)=O)N=2)C=1)(C)(C)C.C(=O)([O-])[O-].[Cs+].[Cs+]>C1(C)C=CC=CC=1.C(OCC)(=O)C.CC([O-])=O.CC([O-])=O.[Pd+2].C1C=CC(P(C2C(C3C(P(C4C=CC=CC=4)C4C=CC=CC=4)=CC=C4C=3C=CC=C4)=C3C(C=CC=C3)=CC=2)C2C=CC=CC=2)=CC=1>[CH3:15][O:14][C:10]1[CH:9]=[C:8]([CH:13]=[CH:12][CH:11]=1)[NH2:7]

Participants

8

Reactant 3

HCID 10796Cesium carbonateHCID 59174316HCID 59174316, compoundHCID 59174704HCID 59174704, compound

Product 1

HCID 108243-MethoxyanilineYield 79.5%

Reagents, catalysts & solvents 4

HCID 167845palladium(II) acetateCatalystHCID 634876Binap, (A+-)-CatalystHCID 1140TolueneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
100 °C

Procedure

To a solution of 6 (1.69 g, 12.26 mmol), in toluene (50.0 mL) was added 7 (2.0 g, 12.26 mmol), BINAP (0.3 g, 0.49 mmol), cesium carbonate (7.9 g, 24.5 mmol). The solution was degassed (by purging N2 for 15 min) and to it was added Pd(OAc)2 (0.054 g, 0.25 mmol). The reaction mixture was stirred at 100° C. for 16 h under nitrogen atmosphere. It was cooled, diluted with ethyl acetate (100 mL) and filtered through Celite®. The filtrate was washed with water (2×25 mL), brine (25 mL), dried over Na2SO4 and concentrated under reduced pressure. The residue obtained was further purified by column chromatography (SiO2, 60-120 mesh, Ethylacetete/hexane: 15/85). The solid obtained after evaporating the required fractions was washed with diethyl ether and dried under high vacuum to get 8 (1.2 g, 37%) as a light yellow solid.

Workup

  1. customThe solution was degassed
  2. custom(by purging N2 for 15 min)
  3. temperatureIt was cooled
  4. filtrationfiltered through Celite®
  5. washThe filtrate was washed with water (2×25 mL), brine (25 mL)
  6. dry with materialdried over Na2SO4
  7. concentrationconcentrated under reduced pressure
  8. customThe residue obtained
  9. customwas further purified by column chromatography (SiO2, 60-120 mesh, Ethylacetete/hexane: 15/85)
  10. customThe solid obtained
  11. customafter evaporating the required fractions
  12. washwas washed with diethyl ether
  13. customdried under high vacuum

Sources & evidence

ORD record
ord-ba761d0d6b694a918d4dbf7566ed9cc9
Source dataset
uspto-grants-2016_08
Patent number
US09409921B2

Reaction notes

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