Methanol → Tert-butyl 3-(5-amino-6-(dibenzylamino)pyrimidin-4-ylamino)phenylcarbamate

HRID 1887039Notes

Reaction equation

HRID 1887039 reaction equation
[CH2:1]([N:8]([CH2:33][C:34]1[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=1)[C:9]1[N:14]=[CH:13][N:12]=[C:11]([NH:15][C:16]2[CH:17]=[C:18]([NH:22][C:23](=[O:29])[O:24][C:25]([CH3:28])([CH3:27])[CH3:26])[CH:19]=[CH:20][CH:21]=2)[C:10]=1[N+:30]([O-])=O)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[NH4+].[Cl-].CO.O>C1COCC1.[Fe]>[NH2:30][C:10]1[C:11]([NH:15][C:16]2[CH:17]=[C:18]([NH:22][C:23](=[O:29])[O:24][C:25]([CH3:27])([CH3:26])[CH3:28])[CH:19]=[CH:20][CH:21]=2)=[N:12][CH:13]=[N:14][C:9]=1[N:8]([CH2:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1)[CH2:33][C:34]1[CH:35]=[CH:36][CH:37]=[CH:38][CH:39]=1

Participants

7

Reactant 4

HCID 887MethanolHCID 962WaterHCID 25517Ammonium ChlorideHCID 86761987tert-Butyl 3-(6-(dibenzylamino)-5-nitropyrimidin-4-ylamino)phenylcarbamate

Product 1

HCID 86691211Tert-butyl 3-(5-amino-6-(dibenzylamino)pyrimidin-4-ylamino)phenylcarbamateYield 46.1%

Reagents, catalysts & solvents 2

HCID 23925IronCatalystHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
50 °C

Procedure

To a solution of tert-butyl 3-(6-(dibenzylamino)-5-nitropyrimidin-4-ylamino)phenylcarbamate (2) (9.2 g, 17.5 mmol) in 100 mL THF were added Fe powder (9.8 g, 175 mmol), NH4Cl (18.7 g, 350 mmol), 100 mL MeOH and 20 mL H2O. The reaction mixture was heated at 50° C. for 7 hrs under N2. After cooling to rt, the reaction mixture was filtered through a pad of Celite. The filtrate was concentrated to 100 mL, and extracted with EtOAc (80 mL×3). The combined organic layer was washed with water (100 mL×2) and brine (100 mL×1), dried over Na2SO4, then concentrated to dryness in vacuo. The residual was purified by column chromatography (silica gel, 0 to 30% ethyl acetate in petroleum ether) to give tert-butyl 3-(5-amino-6-(dibenzylamino)pyrimidin-4-ylamino)phenylcarbamate (3) (4.0 g, 46.1%) as a brown solid. LC-MS (ESI): m/z (M+1) 497.

Workup

  1. temperatureAfter cooling to rt
  2. filtrationthe reaction mixture was filtered through a pad of Celite
  3. concentrationThe filtrate was concentrated to 100 mL
  4. extractionextracted with EtOAc (80 mL×3)
  5. washThe combined organic layer was washed with water (100 mL×2) and brine (100 mL×1)
  6. dry with materialdried over Na2SO4
  7. concentrationconcentrated to dryness in vacuo
  8. customThe residual was purified by column chromatography (silica gel, 0 to 30% ethyl acetate in petroleum ether)

Sources & evidence

ORD record
ord-ffeb8782e7054c4d804bdc0cb5c4e92b
Source dataset
uspto-grants-2013_08
Patent number
US08501724B1

Reaction notes

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