4-Bromo-2-methylaniline → 4-(Dimethylphosphoryl)-2-methylaniline

HRID 1472061Notes

Reaction equation

HRID 1472061 reaction equation
Br[C:2]1[CH:8]=[CH:7][C:5]([NH2:6])=[C:4]([CH3:9])[CH:3]=1.[CH3:10][PH:11](=[O:13])[CH3:12].P([O-])([O-])([O-])=O.[K+].[K+].[K+]>CN(C=O)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.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>[CH3:10][P:11]([C:2]1[CH:8]=[CH:7][C:5]([NH2:6])=[C:4]([CH3:9])[CH:3]=1)([CH3:12])=[O:13]

Participants

7

Reactant 3

HCID 114234-Bromo-2-methylanilineHCID 62657Potassium Phosphate, TribasicHCID 178503022methylphosphonoylmethane

Product 1

HCID 670526834-(Dimethylphosphoryl)-2-methylanilineYield 85.4%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)CatalystHCID 6228DimethylformamideSolvent

Procedure

To a solution of 4-bromo-2-methylaniline (0.372 g, 2.00 mmol) in 8 mL DMF was added dimethylphosphine oxide (0.171 g, 2.20 mmol), palladium acetate (22.4 mg, 0.0100 mmol), XANTPHOS (69.4 mg, 0.120 mmol), and potassium phosphate (0.467 g, 2.20 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 (0-20% 7N ammonia in methanol:dichloromethane) to afford the desired product (0.313 g, 85% yield).

Workup

  1. customThe mixture was purged with nitrogen
  2. concentrationThe reaction mixture was concentrated
  3. custompurified by silica gel chromatography (0-20% 7N ammonia in methanol:dichloromethane)

Sources & evidence

ORD record
ord-13d5b5778c1b4330babb14755ab8e0dd
Source dataset
uspto-grants-2015_04
Patent number
US09012462B2

Reaction notes

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