N-{3-[(2,5-dichloropyrimidin-4-yl)amino]benzyl}-3-nitrobenzamide → 3-Amino-N-{3-[(2,5-dichloropyrimidin-4-yl)amino]benzyl}benzamide

HRID 541817Notes

Reaction equation

HRID 541817 reaction equation
[Cl:1][C:2]1[N:7]=[C:6]([NH:8][C:9]2[CH:10]=[C:11]([CH:25]=[CH:26][CH:27]=2)[CH2:12][NH:13][C:14](=[O:24])[C:15]2[CH:20]=[CH:19][CH:18]=[C:17]([N+:21]([O-])=O)[CH:16]=2)[C:5]([Cl:28])=[CH:4][N:3]=1>O.CO.C(O)(=O)C.[Fe]>[NH2:21][C:17]1[CH:16]=[C:15]([CH:20]=[CH:19][CH:18]=1)[C:14]([NH:13][CH2:12][C:11]1[CH:25]=[CH:26][CH:27]=[C:9]([NH:8][C:6]2[C:5]([Cl:28])=[CH:4][N:3]=[C:2]([Cl:1])[N:7]=2)[CH:10]=1)=[O:24]

Participants

6

Reactant 1

HCID 57961607N-{3-[(2,5-dichloropyrimidin-4-yl)amino]benzyl}-3-nitrobenzamide

Product 1

HCID 579622043-Amino-N-{3-[(2,5-dichloropyrimidin-4-yl)amino]benzyl}benzamideYield 117.2%

Reagents, catalysts & solvents 4

HCID 23925IronCatalystHCID 176Acetic AcidSolventHCID 887MethanolSolventHCID 962WaterSolvent

Conditions

Temperature
0 °C

Procedure

To a solution N-{3-[(2,5-dichloropyrimidin-4-yl)amino]benzyl}-3-nitrobenzamide (400.0 mg, 0.956 mmol) in water (0.7 mL), methanol (3.7 mL) and acetic acid (1.5 mL) was added iron (130 mg, 2.4 mmol) powder in small quantities. When the addition was completed, the very cloudy mixture was stirred at 0° C. for 1 h and then heat at 40° C. for 3 h. The mixture was filtered, and the cake was washed with MeOH/EtOAc. The filtrate was concentrated and the residue was diluted with H2O, then the aqueous layer was extracted with EtOAc three times. The combined organic layers were dried, filtered and concentrated to give the desired product as an off-white powder (435 mg). LCMS for C18H15Cl2N5O (M+H)+: m/z=388.0, 390.0, 392.0. 1H NMR (400 MHz, CD3OD): δ 8.20 (s, 1H), 7.59 (t, J=2.0 Hz, 1H), 7.52 (d, J=8.0 Hz, 1H), 7.36 (t, J=8.0 Hz, 1H), 7.24 (m, 2H), 7.20 (m, 2H), 6.93 (m, 1H), 4.60 (s, 2H).

Workup

  1. additionWhen the addition
  2. temperatureheat at 40° C. for 3 h
  3. filtrationThe mixture was filtered
  4. washthe cake was washed with MeOH/EtOAc
  5. concentrationThe filtrate was concentrated
  6. additionthe residue was diluted with H2O
  7. extractionthe aqueous layer was extracted with EtOAc three times
  8. customThe combined organic layers were dried
  9. filtrationfiltered
  10. concentrationconcentrated

Sources & evidence

ORD record
ord-cae36fe49d1644e8bbde3f145f00ce12
Source dataset
uspto-grants-2014_10
Patent number
US08871753B2

Reaction notes

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