Cesium carbonate → HCID 86681244, compound

HRID 1848270Notes

Reaction equation

HRID 1848270 reaction equation
[NH2:1][C:2]1[CH:7]=[CH:6][C:5]([OH:8])=[CH:4][C:3]=1[N+:9]([O-:11])=[O:10].C(=O)([O-])[O-].[Cs+].[Cs+].[O:18]1[CH2:21][CH:20](OS(C2C=CC(C)=CC=2)(=O)=O)[CH2:19]1>CN(C=O)C>[N+:9]([C:3]1[CH:4]=[C:5]([O:8][CH:20]2[CH2:21][O:18][CH2:19]2)[CH:6]=[CH:7][C:2]=1[NH2:1])([O-:11])=[O:10]

Participants

5

Reactant 3

HCID 10796Cesium carbonateHCID 37588824-Amino-3-NitrophenolHCID 13153907Oxetan-3-yl 4-methylbenzene-1-sulfonate

Product 1

HCID 86681244HCID 86681244, compoundYield 71%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
80 °C

Procedure

To a stirred solution of 4-amino-3-nitrophenol (1.37 g, 8.91 mmol) in DMF (15 mL) at rt was added cesium carbonate (5.79 g, 17.82 mmol) and the mixture was stirred for 30 min. Oxetan-3-yl-4-methylbenzenesulfonate (3.05 g, 13.36 mmol) was added and the mixture was heated at 80° C. for 6 h. The mixture was cooled to rt and partitioned between EtOAc and water. The organic layer was separated, and the aqueous layer was extracted with additional EtOAc. The combined organic layers were washed with brine. The organic layer was separated, dried over MgSO4, filtered, and concentrated under reduced pressure. The solid residue was purified by trituration with diethyl ether to afford 2-nitro-4-(oxetan-3-yloxy)aniline (1.33 g, 71%) as a brown solid. 1H NMR (500 MHz, DMSO-d6) δ 7.29 (br s, 2H), 7.15 (dd, J=9.2, 3.0 Hz, 1H), 7.10 (d, J=3.0 Hz, 1H), 7.02 (d, J=9.2 Hz, 1H), 5.24 (pentet, J=4.9 Hz, 1H), 4.87-4.93 (m, 2H), 4.51-4.53 (m, 2H); LCMS (ESI) m/z 211 (M+H)+.

Workup

  1. temperatureThe mixture was cooled to rt
  2. custompartitioned between EtOAc and water
  3. customThe organic layer was separated
  4. extractionthe aqueous layer was extracted with additional EtOAc
  5. washThe combined organic layers were washed with brine
  6. customThe organic layer was separated
  7. dry with materialdried over MgSO4
  8. filtrationfiltered
  9. concentrationconcentrated under reduced pressure
  10. customThe solid residue was purified by trituration with diethyl ether

Sources & evidence

ORD record
ord-d81b62a2debe41d9a1afde5314530dd7
Source dataset
uspto-grants-2015_02
Patent number
US08952058B2

Reaction notes

Loading…