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

HRID 634072Notes

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]=[C:13]([CH3:17])[C:12]=1[B:18]1[O:22][C:21]([CH3:24])([CH3:23])[C:20]([CH3:26])([CH3:25])[O:19]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]=[C:13]([CH3:17])[C:12]=1[B:18]1[O:19][C:20]([CH3:26])([CH3:25])[C:21]([CH3:24])([CH3:23])[O:22]1

Participants

Conditions

Temperature: 80 °C

Procedure

A mixture of 2.09 g (19.5 mmol) of 2-methylaniline, 4.00 g (13.0 mmol) of 2-[2-(bromomethyl)-6-methylphenyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, and 1.97 g (14.3 mmol) of K2CO3 in 75 ml of DMF was stirred for 12 h at the 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 hexane. Yield 2.60 g (59%) of light-yellow powder. Anal. calc. for C21H28BNO2: C, 74.79; H, 8.37; N, 4.15. Found: C, 74.95; H, 8.52; N, 3.95. 1H NMR (CDCl3): δ 7.22 (m, 1H, 3-H in 6-MeC6H3CH2), 7.16 (m, 1H, 3-H in 6-MeC6H3CH2), 7.12 (m, 1H, 5-H in 2-MeC6H4), 7.09 (m, 1H, 5-H in 6-MeC6H3CH2), 7.04 (m, 1H, 3-H in 2-MeC6H4), 6.71 (m, 1H, 6-H in 2-MeC6H4), 6.66 (m, 1H, 4-H in 2-MeC6H4), 4.34 (d, J=25.3 Hz, 1H, CHH′NH), 4.27 (d, J=25.3 Hz, 1H, CHH′NH), 3.85 (br.s, 1H, NH), 2.46 (s, 3H, Me in 6-MeC6H3CH2), 2.11 (s, 3H, Me in 2-MeC6H4), 1.25 (s, 12H, Bpin).

Workup

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

Sources & evidence

ORD record: ord-5640d9d8714448d0979cf2f8f922b3ba
Source dataset: uspto-grants-2016_04
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09321858B2

Reaction notes

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