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

HRID 634048Notes

Reaction equation

[NH2:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.Br[CH2:9][C:10]1[CH:19]=[CH:18][C:17]2[C:12](=[CH:13][CH:14]=[CH:15][CH:16]=2)[C:11]=1[B:20]1[O:24][C:23]([CH3:26])([CH3:25])[C:22]([CH3:28])([CH3:27])[O:21]1.C([O-])([O-])=O.[K+].[K+].O>CN(C=O)C>[CH3:25][C:23]1([CH3:26])[C:22]([CH3:27])([CH3:28])[O:21][B:20]([C:11]2[C:12]3[C:17](=[CH:16][CH:15]=[CH:14][CH:13]=3)[CH:18]=[CH:19][C:10]=2[CH2:9][NH:1][C:2]2[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=2)[O:24]1

Participants

Conditions

Temperature: 80 °C

Procedure

A mixture of 12.0 g (129 mmol) of aniline, 30.0 g (86.5 mmol) of 2-[2-(bromomethyl)-1-naphthyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, and 13.1 g (94.9 mmol) of K2CO3 in 500 cm3 of DMF was stirred for 12 h at 80° C. The resulting mixture was poured into 1000 cm3 of water. The product was extracted with 3×200 ml of ethyl acetate. The combined extract was dried over MgSO4 and then evaporated to dryness. An excess of aniline was distilled off using Kugelrohr apparatus. Yield 25.3 g (82%). Anal. calc. for C23H26BNO2: C, 76.89; H, 7.29; N, 3.90. Found: C, 77.02; H, 7.45; N, 3.70. 1H NMR (CDCl3): δ 8.19 (m, 1H, 8-H in naphthalene), 7.83 (d, J=8.8 Hz, 1H, 4-H in naphthalene), 7.80 (m, 1H, 5-H in naphthalene), 7.49 (d, J=8.8 Hz, 1H, 3-H in naphthalene), 7.40-7.51 (m, 2H, 6, 7-H in naphthalene), 7.19 (m, 2H, 2, 6-H in Ph), 6.75 (m, 1H, 4-H in Ph), 6.69 (m, 2H, 3, 5-H in Ph), 4.51 (s, 2H, CH2N), 4.07 (br.s, 1H, NH), 1.38 (s, 12H, Me in tetramethyldioxaborolane).

Workup

extractionThe product was extracted with 3×200 ml of ethyl acetate
extractionThe combined extract
dry with materialwas dried over MgSO4
customevaporated to dryness
distillationAn excess of aniline was distilled off

Sources & evidence

ORD record: ord-3c87b4ea52b946ac88681871d6ca689f
Source dataset: uspto-grants-2016_04
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09321858B2

Reaction notes

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