Potassium Phosphate, Tribasic → 4-(Dipropylphosphoryl)-2-methoxyaniline

HRID 1472030Notes

Reaction equation

HRID 1472030 reaction equation
Br[C:2]1[CH:8]=[CH:7][C:5]([NH2:6])=[C:4]([O:9][CH3:10])[CH:3]=1.[CH2:11]([PH:14](=[O:18])[CH2:15][CH2:16][CH3:17])[CH2:12][CH3:13].CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2.P([O-])([O-])([O-])=O.[K+].[K+].[K+]>CN(C=O)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[CH2:11]([P:14]([C:2]1[CH:8]=[CH:7][C:5]([NH2:6])=[C:4]([O:9][CH3:10])[CH:3]=1)([CH2:15][CH2:16][CH3:17])=[O:18])[CH2:12][CH3:13]

Participants

7

Reactant 4

HCID 62657Potassium Phosphate, TribasicHCID 4592574-Bromo-2-methoxyanilineHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 178460678HCID 178460678, compound

Product 1

HCID 670527104-(Dipropylphosphoryl)-2-methoxyaniline

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 6228DimethylformamideSolvent

Procedure

To a solution of 4-bromo-2-methoxyaniline (0.100 g, 0.495 mmol) in 2 mL DMF was added dipropylphosphine oxide (0.0730 g, 0.544 mmol), palladium acetate (5.6 mg, 0.025 mmol), XANTPHOS (17.2 mg, 0.030 mmol), and potassium phosphate (0.116 g, 0.544 mmol). The mixture was purged with nitrogen, and subjected to microwaves at 150° C. for 20 minutes. The reaction mixture was concentrated and purified by silica gel chromatography (0-12% 7N ammonia in methanol:dichloromethane) and the fractions were concentrated. The residue was acidified with 2.5 M HCl in ethanol and the solution was concentrated to provide 4-(dipropylphosphoryl)-2-methoxyaniline as the hydrochloride salt (0.132 g, 91% yield).

Workup

  1. customThe mixture was purged with nitrogen
  2. concentrationThe reaction mixture was concentrated
  3. custompurified by silica gel chromatography (0-12% 7N ammonia in methanol:dichloromethane)
  4. concentrationthe fractions were concentrated
  5. concentrationthe solution was concentrated

Sources & evidence

ORD record
ord-17d5b8a3e873411aa5f4f5857275796f
Source dataset
uspto-grants-2015_04
Patent number
US09012462B2

Reaction notes

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