Water → 2-Methyl-N-[2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzyl]aniline

HRID 634068Notes

Reaction equation

HRID 634068 reaction equation
[CH3:1][C:2]1[CH:8]=[CH:7][CH:6]=[CH:5][C:3]=1[NH2:4].Br[CH2:10][C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][C:12]=1[B:17]1[O:21][C:20]([CH3:23])([CH3:22])[C:19]([CH3:25])([CH3:24])[O:18]1.C([O-])([O-])=O.[K+].[K+].O>CN(C=O)C>[CH3:1][C:2]1[CH:8]=[CH:7][CH:6]=[CH:5][C:3]=1[NH:4][CH2:10][C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][C:12]=1[B:17]1[O:18][C:19]([CH3:25])([CH3:24])[C:20]([CH3:23])([CH3:22])[O:21]1

Participants

6

Reactant 4

HCID 962WaterHCID 7242O-ToluidineHCID 11430Potassium CarbonateHCID 38348342-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)benzyl Bromide

Product 1

HCID 1317354792-Methyl-N-[2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzyl]aniline

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
80 °C

Procedure

A mixture of 1.60 g (15 mmol) of 2-methylaniline, 3.00 g (10 mmol) of 2-[2-(bromomethyl)-phenyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, and 1.52 g (11 mmol) of K2CO3 in 75 ml of DMF was stirred for 12 h at 80° C. The resulting mixture was poured into 300 ml of water. The product was extracted with 3×50 ml of ethyl acetate. The combined extract was dried over Na2SO4 and then evaporated to dryness. An excess of 2-methylaniline was distilled off using Kugelrohr apparatus. The residue was re-crystallized from 20 ml of n-hexane. Yield 1.82 g (56%) of red crystalline powder. Anal. calc. for C20H26BNO2: C, 74.32; H, 8.11; N, 4.33. Found: C, 73.99; H, 8.02; N, 4.45. 1H NMR (CDCl3): δ 7.82 (m, 1H, 5-H in 2-MeC6H4), 7.36-7.41 (m, 2H, 3, 5-H in C6H4CH2), 7.26 (m, 1H, 4-H in C6H4CH2), 7.08 (m, 1H, 5-H in 2-MeC6H4), 7.02 (m, 1H, 3-H in 2-MeC6H4), 6.71 (m, 1H, 6-H in 2-MeC6H4), 6.61 (m, 1H, 4-H in 2-MeC6H4), 4.55 (br.s, 2H, CH2NH), 4.31 (br.s, 1H, NH), 2.13 (s, 3H, Me in 2-MeC6H4), 1.31 (s, 12H, Bpin).

Workup

  1. extractionThe product was extracted with 3×50 ml of ethyl acetate
  2. extractionThe combined extract
  3. dry with materialwas dried over Na2SO4
  4. customevaporated to dryness
  5. distillationAn excess of 2-methylaniline was distilled off
  6. customThe residue was re-crystallized from 20 ml of n-hexane

Sources & evidence

ORD record
ord-afaa697bf57d4f50b62b36434d0f5508
Source dataset
uspto-grants-2016_04
Patent number
US09321858B2

Reaction notes

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