Water → HCID 21914155, compound

HRID 1988308Notes

Reaction equation

HRID 1988308 reaction equation
Br[C:2]1[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[CH:5]=[CH:4][C:3]=1[O:11][CH3:12].Cl.[NH2:14][CH2:15][C:16]1[CH:21]=[CH:20][C:19](B(O)O)=[CH:18][CH:17]=1.[Na].O>C(O)CC.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[NH2:14][CH2:15][C:16]1[CH:21]=[CH:20][C:19]([C:2]2[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[CH:5]=[CH:4][C:3]=2[O:11][CH3:12])=[CH:18][CH:17]=1

Participants

8

Reactant 4

HCID 962WaterHCID 788702-Bromo-4-nitroanisoleHCID 27343114-Aminomethylphenylboronic acid hydrochlorideHCID 5360545Sodium

Product 1

HCID 21914155HCID 21914155, compoundYield 71.2%

Reagents, catalysts & solvents 3

HCID 11776TriphenylphosphineCatalystHCID 167845palladium(II) acetateCatalystHCID 10311-PropanolSolvent

Conditions

Temperature
95 °C

Procedure

A mixture of 2-bromo-4-nitroanisole (5.80 g, 25.0 mmol) and 4-(aminomethyl)phenylboronic acid hydrochloride (4.96 g, 26.6 mmol) was slurried in 1-propanol (50 mL) under nitrogen. Triphenylphosphine (315 mg, 1.20 mmol) and palladium (II) acetate (90 mg, 0.40 mmol) were added, followed by 2.0N sodium carabonate (33 mL, 66 mmol). The mixture was heated at 95° C. (oil bath) under nitrogen for 3 hours, at which time the reaction was judged to be complete by TLC. Water (25 mL) was added and the mixture was stirred open to air for 2 hours at room temperature. The mixture was extracted with ethyl acetate (100 mL, 2×50 mL) and the combined extracts were washed with sodium bicarbonate (25 mL) and brine (25 mL). The solution was dried with sodium sulfate, and concentrated to an oil which was purified by flash chromatography on silica gel (100 g) eluting with 0-4% methanol/0,5% triethylamine/dichloromethane. Pure fractions were combined and concentrated to give 2-(4-aminomethylphenyl)-4-nitroanisole (4.6 g) as a yellow solid.

Workup

  1. extractionThe mixture was extracted with ethyl acetate (100 mL, 2×50 mL)
  2. washthe combined extracts were washed with sodium bicarbonate (25 mL) and brine (25 mL)
  3. dry with materialThe solution was dried with sodium sulfate
  4. concentrationconcentrated to an oil which
  5. customwas purified by flash chromatography on silica gel (100 g)
  6. washeluting with 0-4% methanol/0,5% triethylamine/dichloromethane
  7. concentrationconcentrated

Sources & evidence

ORD record
ord-cc600199232447099be17182dc4b35a2
Source dataset
uspto-grants-2009_06
Patent number
US07553971B2

Reaction notes

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