Hydrazine hydrate (1:1) → HCID 68667054, compound

HRID 1716835Notes

Reaction equation

HRID 1716835 reaction equation
[N+:1]([C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][C:5]=1[NH:10][C:11]1[CH:20]=[CH:19][C:14]([C:15]([O:17][CH3:18])=[O:16])=[CH:13][CH:12]=1)([O-])=O.O.NN>CO.[Pd]>[CH3:18][O:17][C:15](=[O:16])[C:14]1[CH:13]=[CH:12][C:11]([NH:10][C:5]2[CH:6]=[CH:7][CH:8]=[CH:9][C:4]=2[NH2:1])=[CH:20][CH:19]=1

Participants

5

Reactant 2

HCID 24654Hydrazine hydrate (1:1)HCID 57550196HCID 57550196, compound

Product 1

HCID 68667054HCID 68667054, compoundYield 80%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 887MethanolSolvent

Procedure

A solution of methyl 4-[(2-nitrophenyl)amino]benzoate (20 g, 48 mmol) in methanol under nitrogen was treated with 5% Pd/C (1.8 g, 30 w/v) and hydrazine hydrate (11.7 g, 230 mmol), heated at reflux temperature for 2 h, cooled to room temperature and filtered. The filtrate was concentrated under reduced pressure. The resultant residue was partitioned between CH2Cl2 and water. The organic phase was separated, dried over Na2SO4 and concentrated under vacuum. The resultant residue was purified with flash column chromatography with (silica, EtOAc:hexanes 4:6) to give 4-(2-aminophenylamino)benzoic acid methyl ester in 80% yield, 1H NMR (400 MHz, CDCl3): 7.87 (d, J=8.8 Hz, 2H), 7.13 (d, J=8.0 Hz, 1H) 7.09 (t, J=8 Hz, 1H), 6.82 (d, J=8.0 Hz, 1H), 6.78 (t, J=8 Hz, 1H), 6.67 (d, J=8.0 Hz, 2H), 5.4 (bs, 1H), 3.8 (s, 3H), 3.71 (s, 2H); LCMS (ESI+) 243 (MH+).

Workup

  1. temperatureheated
  2. temperatureat reflux temperature for 2 h
  3. filtrationfiltered
  4. concentrationThe filtrate was concentrated under reduced pressure
  5. customThe resultant residue was partitioned between CH2Cl2 and water
  6. customThe organic phase was separated
  7. dry with materialdried over Na2SO4
  8. concentrationconcentrated under vacuum
  9. customThe resultant residue was purified with flash column chromatography with (silica, EtOAc:hexanes 4:6)

Sources & evidence

ORD record
ord-237ee2bedf4f4434a0c04e5cacdba26c
Source dataset
uspto-grants-2010_09
Patent number
US07803825B2

Reaction notes

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