Triethylamine → HCID 57677766, compound

HRID 492706Notes

Reaction equation

HRID 492706 reaction equation
[CH3:1][C:2]1[CH:3]=[C:4]([CH:13]=[CH:14][C:15]=1[N+:16]([O-])=O)[O:5][C:6]1[CH:11]=[CH:10][N:9]=[C:8]([NH2:12])[CH:7]=1.[CH2:19]([N:21]([CH2:24][CH3:25])[CH2:22]C)[CH3:20].ClC(OC1C=CC=CC=1)=[O:28].N1CCCC1.[Cl-].[NH4+]>O1CCCC1.[Fe].O.CN(C)C=O>[NH2:16][C:15]1[CH:14]=[CH:13][C:4]([O:5][C:6]2[CH:11]=[CH:10][N:9]=[C:8]([NH:12][C:22]([N:21]3[CH2:24][CH2:25][CH2:20][CH2:19]3)=[O:28])[CH:7]=2)=[CH:3][C:2]=1[CH3:1]

Participants

10

Reactant 5

HCID 8471TriethylamineHCID 15891Phenyl chloroformateHCID 25517Ammonium ChlorideHCID 31268PyrrolidineHCID 23153294HCID 23153294, compound

Product 1

HCID 57677766HCID 57677766, compoundYield 39.2%

Reagents, catalysts & solvents 4

HCID 23925IronCatalystHCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
80 °C

Procedure

To a solution of 4-(3-methyl-4-nitrophenoxy)pyridin-2-ylamine (553 mg, 2.26 mmol) in tetrahydrofuran (20 ml) was added triethylamine (0.471 ml, 3.38 mmol) under a nitrogen atmosphere. Phenyl chloroformate (0.424 ml, 3.38 mmol) was added thereto while ice-cooling, followed by stirring for 20 min. The reaction mixture was concentrated under a reduced pressure to give a residue, to which N,N-dimethylformamide (8.0 ml) and pyrrolidine (0.753 ml, 9.02 mmol), followed by stirring at room temperature for 10 min. The reaction mixture was partitioned between ethyl acetate (60 ml) and water (60 ml). The organic layer was washed with brine, dried over anhydrous sodium sulfate, and concentrated under a reduced pressure. The resultant residue was dissolved in ethanol (20 ml), and then electrolytic iron powder (505 mg, 9.04 mmol), ammonium chloride (967 ml, 18.1 mmol) and water (5 ml) were added thereto, followed by stirring to heat at 80° C. for 2 hrs. The reaction mixture was cooled down to room temperature, and filtered to remove an insoluble portion. The filtrate was concentrated under a reduced pressure to give a residue, which was then purified by silica gel column chromatography (eluent; hexane/ethyl acetate=1/1, ethyl acetate, then ethyl acetate/methanol=10/1) to provide the titled compound (277 mg, 39.2%) as orange powder.

Workup

  1. temperaturewhile ice-cooling
  2. concentrationThe reaction mixture was concentrated under a reduced pressure
  3. customto give a residue
  4. stirringby stirring at room temperature for 10 min
  5. customThe reaction mixture was partitioned between ethyl acetate (60 ml) and water (60 ml)
  6. washThe organic layer was washed with brine
  7. dry with materialdried over anhydrous sodium sulfate
  8. concentrationconcentrated under a reduced pressure
  9. dissolutionThe resultant residue was dissolved in ethanol (20 ml)
  10. stirringby stirring
  11. temperatureThe reaction mixture was cooled down to room temperature
  12. filtrationfiltered
  13. customto remove an insoluble portion
  14. concentrationThe filtrate was concentrated under a reduced pressure
  15. customto give a residue, which
  16. customwas then purified by silica gel column chromatography (eluent

Sources & evidence

ORD record
ord-39123073afb84baebcbd05ebac3bbf28
Source dataset
uspto-grants-2009_05
Patent number
US07531532B2

Reaction notes

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