4-Bromoanisole → N-(4-Methoxyphenyl)-5-nitro-2-pyrimidinamine

HRID 1662858Notes

Reaction equation

HRID 1662858 reaction equation
[N+:1]([C:4]1[CH:5]=[N:6][C:7]([NH2:10])=[N:8][CH:9]=1)([O-:3])=[O:2].Br[C:12]1[CH:17]=[CH:16][C:15]([O:18][CH3:19])=[CH:14][CH:13]=1.C(=O)([O-])[O-].[Cs+].[Cs+].C1(P(C2C=CC=CC=2)C2C3OC4C(=CC=CC=4P(C4C=CC=CC=4)C4C=CC=CC=4)C(C)(C)C=3C=CC=2)C=CC=CC=1>[Pd].[Pd].C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1.C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1.C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1>[CH3:19][O:18][C:15]1[CH:16]=[CH:17][C:12]([NH:10][C:7]2[N:8]=[CH:9][C:4]([N+:1]([O-:3])=[O:2])=[CH:5][N:6]=2)=[CH:13][CH:14]=1

Participants

6

Reactant 4

HCID 77304-BromoanisoleHCID 10796Cesium carbonateHCID 764905-Nitropyrimidin-2-amineHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)

Product 1

HCID 59652738N-(4-Methoxyphenyl)-5-nitro-2-pyrimidinamine

Reagents, catalysts & solvents 1

HCID 9832798Tris(dibenzylideneacetone) dipalladiumCatalyst

Procedure

In a dry 50 mL round bottom flask 5-nitro-pyrimidin-2-ylamine (1.16 g, 8.3 mmol, 1 equiv), 4-bromo anisole (1.3 mL, 10.4 mmol, 1.25 equiv), cesium carbonate (5.4 g, 16.6 mmol, 2 equiv), 4,5-bis(diphenylphosphino)-9,9-dimethyl xanthene (0.479 g, 0.83 mmol, 0.1 equiv) and tris(dibenzylideneacetone) dipalladium (0.304 g, 0.33 mmol, 0.04 equiv) were combined. Reactants were flushed with argon, diluted with dioxane (15 mL) and outfitted with reflux condenser. Reaction was heated to reflux for 18 hours. Reaction was then filtered hot and solvents were evaporated to provide dark solids. Silica gel chromatography (1:4 EtOAc/Hexanes) provided desired product. Yellow powder (0.6 g, 30% yield). Rf=0.39 (20% EtOAc/Hexanes).

Workup

  1. customReactants were flushed with argon
  2. additiondiluted with dioxane (15 mL)
  3. temperaturewith reflux condenser
  4. customReaction
  5. temperaturewas heated
  6. temperatureto reflux for 18 hours
  7. customReaction
  8. filtrationwas then filtered hot
  9. customsolvents were evaporated
  10. customto provide dark solids

Sources & evidence

ORD record
ord-b238b3970039412babfb9272e84ea5dc
Source dataset
uspto-grants-2011_10
Patent number
US08030487B2

Reaction notes

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