4-Bromo-3-methylaniline → 3-Methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline

HRID 723191Notes

Reaction equation

HRID 723191 reaction equation
Br[C:2]1[CH:8]=[CH:7][C:5]([NH2:6])=[CH:4][C:3]=1[CH3:9].[CH3:10][C:11]1([CH3:18])[C:15]([CH3:17])([CH3:16])[O:14][BH:13][O:12]1>Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[CH3:9][C:3]1[CH:4]=[C:5]([NH2:6])[CH:7]=[CH:8][C:2]=1[B:13]1[O:14][C:15]([CH3:17])([CH3:16])[C:11]([CH3:18])([CH3:10])[O:12]1

Participants

4

Reactant 2

HCID 233594-Bromo-3-methylanilineHCID 27347684,4,5,5-Tetramethyl[1,3,2]dioxaborolane

Product 1

HCID 177502103-Methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)anilineYield 46%

Reagents, catalysts & solvents 1

HCID 178418476HCID 178418476, compoundCatalyst

Conditions

Temperature
95 °C

Procedure

To an oven-dried round bottom flask fitted with a stir bar was added 4-bromo-3-methylaniline (5.7 gm, 31 mmol), 4,4,5,5-tetramethyl-1,3,2-dioxaborolane (13.3 mL, 92 mmol, Aldrich Chemical Company), and PdCl2(PPh3)2 (2.2 gm, 3.1 mmol, Strem Chemicals Inc, Newburyport, Mass.). The flask was sealed with a rubber septum, purged with Argon, and then charged with dry dioxane (100 mL) and triethylamine (26 mL). The reaction mixture was stirred vigorously at 95° C. for 16 h. After cooling to rt, the dioxane was removed in vacuo and the residue was partitioned between EtOAc (200 mL) and water (100 mL). The organic layer was washed with saturated NaHCO3 (2×75 mL), brine (50 mL), and was dried over MgSO4. Removal of the solvents in vacuo followed by flash chromatography of the residue yielded the product (3.3 gm, 46%) as a tan oil. 1H-NMR (CDCl3; 400 MHz): δ 7.61–7.64 (m, 1H), 6.48–6.58 (m, 2H), 3.60–3.90, (br s, 2H), 2.49 (s, 3H), 1.34 (s, 12H). ESI-MS (m/z): Calcd. for C13H20BNO2: 234.1 (M+H); found: 234.2

Workup

  1. customTo an oven-dried round bottom flask fitted with a stir bar
  2. customThe flask was sealed with a rubber septum
  3. custompurged with Argon
  4. additioncharged with dry dioxane (100 mL) and triethylamine (26 mL)
  5. temperatureAfter cooling to rt
  6. customthe dioxane was removed in vacuo
  7. customthe residue was partitioned between EtOAc (200 mL) and water (100 mL)
  8. washThe organic layer was washed with saturated NaHCO3 (2×75 mL), brine (50 mL)
  9. dry with materialwas dried over MgSO4
  10. customRemoval of the solvents in vacuo

Sources & evidence

ORD record
ord-3e263c8cddd04b0bad7e8eb42e91f4ef
Source dataset
uspto-grants-2006_11
Patent number
US07138530B2

Reaction notes

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