Ammonium formate → 4-(2-amino-pyrimidin-5-yl)-N1-tert-butyl-benzene-1,2-diamine

HRID 1966667Notes

Reaction equation

HRID 1966667 reaction equation
[C:1]([NH:5][C:6]1[CH:11]=[CH:10][C:9]([C:12]2[CH:13]=[N:14][C:15]([NH2:18])=[N:16][CH:17]=2)=[CH:8][C:7]=1[N+:19]([O-])=O)([CH3:4])([CH3:3])[CH3:2].C([O-])=O.[NH4+]>CCO.[Zn]>[NH2:18][C:15]1[N:16]=[CH:17][C:12]([C:9]2[CH:8]=[C:7]([NH2:19])[C:6]([NH:5][C:1]([CH3:3])([CH3:2])[CH3:4])=[CH:11][CH:10]=2)=[CH:13][N:14]=1

Participants

5

Reactant 2

HCID 2723923Ammonium formateHCID 58542060HCID 58542060, compound

Product 1

HCID 585418994-(2-amino-pyrimidin-5-yl)-N1-tert-butyl-benzene-1,2-diamineYield 87.4%

Reagents, catalysts & solvents 2

HCID 23994ZincCatalystHCID 702EthanolSolvent

Conditions

Temperature
50 °C

Procedure

To a round bottom flask are added 5-(4-tert-butylamino-3-nitro-phenyl)-pyrimidin-2-ylamine (6.3 g, 0.02 mol) and ammonium formate (6.9 g, 0.1 mol) in EtOH, (100 mL), followed by the addition of zinc dust (4.3 g, 0.066 mol). The reaction mixture is stirred at 50° C. for 2 hours. The reaction mixture is filtered through a short pad of diatomaceous earth. The filter pad is rinsed with MeOH (50 mL) and the combined filtrate is concentrated. The residue is extracted with H2O (50 mL) and EtOAc (3×50 mL). The combined organic layer is washed with saturated NaHCO3 solution (30 mL), dried (MgSO4) and filtered. The filtrate is concentrated to afford 4-(2-amino-pyrimidin-5-yl)-N1-tert-butyl-benzene-1,2-diamine as a dark purple solid (4.5 g, 80%). LCMS (ESMS): m/z 258.20 (M++1)

Workup

  1. filtrationThe reaction mixture is filtered through a short pad of diatomaceous earth
  2. washThe filter pad is rinsed with MeOH (50 mL)
  3. concentrationthe combined filtrate is concentrated
  4. extractionThe residue is extracted with H2O (50 mL) and EtOAc (3×50 mL)
  5. washThe combined organic layer is washed with saturated NaHCO3 solution (30 mL)
  6. dry with materialdried (MgSO4)
  7. filtrationfiltered
  8. concentrationThe filtrate is concentrated

Sources & evidence

ORD record
ord-e8bd6b6ed68a496489f285c882aa2e0a
Source dataset
uspto-grants-2013_04
Patent number
US08420655B2

Reaction notes

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