Water → 2,4,6-Trimethyl-N-{[1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-naphthyl]methyl}aniline

HRID 634049Notes

Reaction equation

HRID 634049 reaction equation
[CH3:1][C:2]1[CH:8]=[C:7]([CH3:9])[CH:6]=[C:5]([CH3:10])[C:3]=1[NH2:4].Br[CH2:12][C:13]1[CH:22]=[CH:21][C:20]2[C:15](=[CH:16][CH:17]=[CH:18][CH:19]=2)[C:14]=1[B:23]1[O:27][C:26]([CH3:29])([CH3:28])[C:25]([CH3:31])([CH3:30])[O:24]1.C([O-])([O-])=O.[K+].[K+].O>CN(C=O)C>[CH3:1][C:2]1[CH:8]=[C:7]([CH3:9])[CH:6]=[C:5]([CH3:10])[C:3]=1[NH:4][CH2:12][C:13]1[CH:22]=[CH:21][C:20]2[C:15](=[CH:16][CH:17]=[CH:18][CH:19]=2)[C:14]=1[B:23]1[O:27][C:26]([CH3:29])([CH3:28])[C:25]([CH3:31])([CH3:30])[O:24]1

Participants

6

Reactant 4

HCID 962WaterHCID 69132,4,6-TrimethylanilineHCID 11430Potassium CarbonateHCID 667958652-[2-(Bromomethyl)-1-naphthyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane

Product 1

HCID 667957632,4,6-Trimethyl-N-{[1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-naphthyl]methyl}aniline

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
80 °C

Procedure

A mixture of 29.2 g (216 mmol) of 2,4,6-trimethylaniline, 50.0 g (144 mmol) of 2-[2-(bromomethyl)-1-naphthyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, and 22.0 g (159 mmol) of K2CO3 in 1100 cm3 of DMF was stirred for 12 h at 80° C. The resulting mixture was poured into 2000 cm3 of water. The product was extracted with 3×400 ml of ethyl acetate. The combined extract was dried over MgSO4 and then evaporated to dryness. The product was isolated by flash chromatography on silica gel 60 (40-63 um; eluent: dichloromethane). Yield 45.0 g (78%). Anal. calc. for C26H32BNO2: C, 77.81; H, 8.04; N, 3.49. Found: C, 78.00; H, 8.24; N, 3.26. 1H NMR (CDCl3): δ 8.27 (m, 1H, 8-H in naphthyl), 7.84 (m, 1H, 5-H in naphthyl), 7.81 (d, J=8.3 Hz, 1H, 4-H in naphthyl), 7.54 (m, 1H, 7-H in naphthyl), 7.48 (m, 1H, 6-H in naphthyl), 7.37 (d, J=8.3 Hz, 1H, 3-H in naphthyl), 6.87 (s, 2H, 3, 5-H in mesityl), 4.39 (s, 2H, CH2N), 3.68 (br.s, 1H, NH), 2.31 (s, 6H, 2, 6-Me in mesityl), 2.30 (s, 3H, 4-Me in mesityl), 1.49 (s, 12H, Me in tetramethyldioxaborolane).

Workup

  1. extractionThe product was extracted with 3×400 ml of ethyl acetate
  2. extractionThe combined extract
  3. dry with materialwas dried over MgSO4
  4. customevaporated to dryness
  5. customThe product was isolated by flash chromatography on silica gel 60 (40-63 um; eluent: dichloromethane)

Sources & evidence

ORD record
ord-f96fd4bd222d46889fe07ba0a08f007a
Source dataset
uspto-grants-2016_04
Patent number
US09321858B2

Reaction notes

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